JP2005200599A - New compound, coloring composition, inkjet printing liquid and inkjet printing method and thermal ink transfer material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition composed of a new compound that exhibits neutral black of high density and an inkjet printing liquid having good light fastness and excellent color reproducibility, to provide an aqueous inkjet printing liquid superior in storage stability of the ink, and to provide an inkjet printing method using the inkjet printing liquid and a highly sensitive thermal ink transfer material that exhibits high density with a little applied energy and excellent image fastness property such as light fastness property. <P>SOLUTION: This compound is represented by general formula (1), wherein Ar<SB>1</SB>represents an aryl group or a heterocyclic group, R<SB>1</SB>represents a hydrogen atom or a substituent, and R<SB>2</SB>represents a substituent, with a proviso that at least one of R<SB>1</SB>and R<SB>2</SB>represents a chromatic portion with a chromophore. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a novel azomethine dye compound, a coloring composition containing the same, an ink jet recording liquid, a thermal transfer recording material, and an ink jet recording method using the ink jet recording liquid.

  Azomethine dyes have been widely used in the field of dyeing fibers and the like, or as dyes and dyes for image formation. On the other hand, in recent years, new color image forming methods such as an ink jet recording method, a thermal transfer method, color electrophotography, printing ink, and a recording pen have been put into practical use.

  Inkjet recording methods include a method in which droplets are pressure-discharged by electro-mechanical conversion of piezoelectric elements, a method in which bubbles are generated by pressure generation by electro-thermal conversion, a method in which droplets are sucked and discharged by electrostatic force, etc. Is usually used.

  In an inkjet recording liquid (hereinafter, also referred to as inkjet ink or simply ink), it conforms to a recording method selected from the above, has a high recorded image density, good color tone, light resistance, It has excellent color image fastness such as heat resistance and water resistance, fast fixing on the recording medium, no bleeding after recording, excellent storability as ink, and safety such as toxicity and flammability. It is required to be free and inexpensive.

  From this point of view, various ink jet recording liquids have been proposed and studied. However, ink jet recording liquids that satisfy many of the requirements simultaneously are extremely limited.

  As for the black ink for ink jet recording, an example using a pigment dispersed ink such as carbon black has been increasing in recent years. However, the pigment-dispersed ink is superior to the water-soluble dye ink in terms of fastness, but has a drawback that the printed image is not glossy and a good image is difficult to obtain when combined with the water-soluble color dye ink. . For this reason, water-soluble black dye ink is often used for photographic quality inkjet images. However, water-soluble black dyes are difficult to obtain a pure black color compared to pigment-dispersed inks, and light resistance is inferior, so improvement is required. In order to improve the color reproducibility and light resistance of black ink, some research and development has already been conducted on a method of obtaining a pure black color by mixing a color dye with an existing black dye. For example, Japanese Patent Publication No. 5-13996 discloses a method of using hood black 2 and one or more red dyes, and Japanese Patent Publication No. 5-13997 uses hood black 2 and one or more of yellow dyes together. Further, Japanese Patent Publication No. 5-13998 proposes a method using a combination of food black 2 and one or more red dyes and one or more yellow dyes, thereby improving color reproducibility. It is reported that the light resistance has also been improved.

  However, with these methods, it is possible to obtain pure black for the ink and its printed image, but for the printed image after photobleaching, the color fading proceeds in the reddish direction even in the case of ink containing only hood black 2. In addition, since a red dye or a yellow dye is mixed, red / yellowness is further increased, and a large change in hue becomes a problem. Japanese Patent Application Laid-Open No. 60-86178 proposes a method of using hood black 2 and one or more blue dyes in combination. This is because the printed image is a blue black color, Not suitable for color tone.

  By the way, conventionally, a bisazo dye has been proposed as a black ink. However, conventionally known black pigments have problems such as low density, neutral hue, and poor image fastness. Some black pigments have a structure having harmful chromium ions in the molecule, which is problematic in terms of safety for human animals. Further, C.I. described in JP-A-2-36277 and JP-A-2-36278. I. (Color Index) Acid Black 140 and C.I. I. There is Acid Black 187. However, the C.I. I. Acid Black 140 and C.I. I. Since Acid Black 187 contains heavy metals, there is a concern about safety. Carbon black, C.I. described in JP-A-1-263165. I. Direct Black 62, C.I. described in JP-A-5-125315. I. Direct black 154 and C.I. described in JP-A No. 63-139963. I. Food black 2 and the like are also used as a pigment for black ink, but have a drawback that the ink discharge port is easily clogged. Therefore, C.I. I. Conventionally well-known dyes and pigments to which numbers are assigned have a problem that the characteristics required for the dyes used in ink jet inks are not sufficiently satisfied.

  As described above, the water-soluble black dye ink for inkjet recording is excellent in color reproducibility and light resistance, particularly excellent in color tone after photobleaching, and has excellent image quality close to a photograph and high reliability. At present, the ink for use has not been obtained yet.

  On the other hand, in recent years, ink jet recording inks have been proposed to color water-dispersible resins with oil-soluble or hydrophobic dyes in order to solve the problem of low water resistance and light fastness of water-based inks using water-soluble dyes. It has been made as. For example, an emulsion polymerization in which a black oil-soluble dye is dissolved in a hydrophobic high-boiling organic solvent and dispersed in an aqueous medium (for example, see Patent Documents 1 and 2) is also dyed with the oil-soluble dye. Inks using particles or dispersed polymer particles (for example, see Patent Documents 3, 4, and 5) have been proposed.

  However, the ink using the oil-soluble dye is inferior in ink stability because the particles are likely to aggregate and settle. In addition, there is a drawback in the hue when printed, and there is a disadvantage that the printing density is low, and further improvement has been desired.

  On the other hand, in the thermal transfer recording material, the black ink layer is designed so that light absorption is performed by covering several visible light regions by containing several kinds of dyes having different maximum absorption wavelengths. However, in the density gradation change due to the change in applied energy, the heat transferability due to the applied energy of each dye is different, so there is a difference in color tone between the low density part and the high density part, and the light resistance of the dye by light irradiation Since the properties are also different, there is a difference in color tone between the low density portion and the high density portion, and it is difficult to obtain a stable neutral gray.

Further, in the case of a black image forming material using several kinds of dyes, it is necessary to contain the dye in the ink layer at a high concentration to obtain a flat black color. There is a problem in that a dye is deposited or a blocking occurs during storage or transportation of the material, resulting in deterioration of storage stability.
JP 2002-20665 A JP 2002-338837 A JP-A-8-253720 JP-A-8-92513 JP-A-8-183920

  A first object of the present invention is to provide a high-concentration, neutral, black-colored coloring composition comprising a novel compound and an ink jet recording liquid exhibiting good light resistance and excellent color reproducibility. The second object is to provide an aqueous ink jet recording liquid having excellent ink storage stability in addition to the first object, and the third object is to provide an ink jet recording method using the ink jet recording liquid. Furthermore, a fourth object is to provide a high-sensitivity thermal transfer recording material that exhibits a high density even with a small applied energy and is excellent in image fastness such as light fastness.

  As a result of various investigations on the above problems, the present inventors have found that a novel compound (azomethine compound) exhibiting excellent performance as a black pigment, a colored composition containing the compound, and an ink jet containing the compound The present inventors have found that the above problems can be solved by using a recording liquid, an ink jet recording method for recording using the ink jet recording liquid, and the use of the compound as a thermal transfer recording material, and have completed the present invention.

(Claim 1)
A compound represented by the following general formula [1].

[Wherein, Ar ₁ represents an aryl group or a heterocyclic group, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a substituent. However, at least one of R ₁ or R ₂ represents a dye moiety having a chromophore. ]
(Claim 2)
The compound represented by the general formula [1] is represented by the following general formula [2].

[In the formula, Ar ₁ represents an aryl group or a heterocyclic group, X represents an oxygen atom or N—R ₅ , R ₃ , R ₄ , R ₅ represent a substituent, and n represents an integer of 1 to 5] Represent. However, at least one of R ₃ , R ₄ or R ₅ represents a dye moiety having a chromophore, and R ₃ and R ₅ may be bonded to each other to form a heterocyclic ring, and when n is 2 or more , R ₄ may be the same or different. ]
(Claim 3)
At least one chromophore of R ₁ or R ₂ represented by the general formula [1] and at least one chromophore of R ₃ , R ₄ or R ₅ represented by the general formula [2] are: The compound according to claim 1 or 2, which is represented by the general formula [3], [4] or [5].

[Wherein, L ₁ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent, and X ₁ represents a coupler residue. ]

[In the formula, L ₂ represents a simple bond or a divalent linking group, R ₇ represents a substituent, m represents an integer of 0 to 7, Y represents an oxygen atom, ═CR ₈ R ₉ — or = NR ₁₀ -is represented, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a substituent, and R ₇ , R ₈ , R ₉ and R ₁₀ may be bonded to each other to form a ring. ]

[In the formula, L ₃ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent, X ₂ represents a coupler residue, Z represents —N═ or —CR ₁₁ ═, R ₁₁ represents a hydrogen atom or a substituent. ]
(Claim 4)
The coloring composition characterized by containing at least 1 sort (s) among the compounds of any one of Claims 1-3.

(Claim 5)
An ink jet recording liquid comprising at least one of the compounds according to claim 1.

(Claim 6)
The ink jet recording liquid according to claim 5, wherein the compound according to claim 1 has a sulfo group or a salt thereof.

(Claim 7)
The ink jet recording liquid according to claim 5, wherein the compound according to any one of claims 1 to 3 is contained as a fine particle dispersion.

(Claim 8)
The ink jet recording liquid according to claim 7, wherein the fine particle dispersion contains an oil-soluble polymer.

(Claim 9)
The inkjet recording liquid according to claim 5, comprising a polyhydric alcohol.

(Claim 10)
10. An ink jet recording method, wherein recording is performed using the ink jet recording liquid according to any one of claims 5 to 9.

(Claim 11)
A thermal transfer recording material comprising at least one of the compounds according to claim 1.

  According to the present invention, it is possible to provide an ink jet recording liquid in which a color image has good light resistance, excellent color reproducibility, and an aqueous ink jet recording liquid excellent in ink storage stability. Furthermore, it was possible to provide a thermal transfer recording material excellent in dye transfer property and light resistance.

  Hereinafter, the present invention will be described in detail.

  The compounds represented by the general formulas [1] and [2] of the present invention (hereinafter also simply referred to as dyes) will be described in detail.

In the general formulas [1] and [2], Ar ₁ represents an aryl group or a heterocyclic group.

  Preferred examples of the aryl group or heterocyclic group include benzene ring, furan ring, pyrrole ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, thiadiazole ring, oxazole ring, thiazole ring, pyran ring, pyridine ring, pyridazine. Ring, pyrimidine ring, pyrazine ring, triazine ring, naphthalene ring, benzofuran ring, indole ring, benzothiophene ring, benzimidazole ring, benzothiazole ring, benzoxazole ring, purine ring, quinoline ring, isoquinoline ring, coumarin ring, chromone ring Examples include groups derived from a 3H-pyrrole ring, 3H-pyrrolidine ring, oxazolidine ring, imidazolidine ring, thiazolidine ring, 3H-indole ring, indandione ring and the like. More preferred are groups derived from a benzene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyramidine ring, pyrazine ring, imidazole ring and thiazole ring, and particularly preferred are groups derived from a benzene ring and a pyridine ring. .

  These rings may further form a condensed ring with another carbocycle (for example, benzene ring) or a heterocycle (for example, pyridine ring). Examples of substituents on the ring include alkyl groups, aryl groups, heterocyclic groups, acyl groups, amino groups, nitro groups, cyano groups, acylamino groups, alkoxy groups, hydroxy groups, alkoxycarbonyl groups, halogen atoms, etc. The group may be further substituted.

In the general formula [1], R ₁ represents a hydrogen atom or a substituent.

  Examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group, dodecyl group, etc.), cycloalkyl group (for example, cyclopentyl group). Group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), alkenyl group (eg, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1 -Methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group etc.), alkyl Sulfonyl group (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl Group (for example, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl group (for example, methylsulfinyl group, etc.), arylsulfinyl group (for example, phenylsulfinyl group, etc.), phosphono group, acyl group (acetyl group, pivaloyl group, Benzoyl group etc.), carbamoyl group (eg aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group etc.), sulfamoyl group ( For example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group, octyl Nosuruhoniru group, dodecyl aminosulfonyl group, a phenyl aminosulfonyl group, naphthyl aminosulfonyl group, 2-pyridyl aminosulfonyl group, etc.), and each group such as a sulfonic acid group.

In the general formula [1], R ₁ is preferably a substituent having a Hammett's substituent constant σP of 0.2 or more. The Hammett's substituent constant σp value used in this specification will be described briefly. Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, "Lange's Handbook of Chemistry", 12th edition, 1979 (Mc Graw-Hill) and "Areas in Chemistry", Special Issue 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. Rather, it also includes substituents that would be included within that range when measured based on Hammett's law, even if the value is unknown.

In the general formula [1], R ₂ represents a substituent, and examples of the substituent include the same groups as R ₁ in the general formula [1].

In the general formula [1], R ₂ is preferably an alkyl group, an aryl group, or a heterocyclic group.

  It is particularly preferred when the compound represented by the general formula [1] is represented by the general formula [2].

In the general formula [2], R ₃ represents a substituent, and examples of the substituent include an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group, hexyl group, octyl group). Group, dodecyl group, etc.), cycloalkyl group (eg, cyclopentyl group, cyclohexyl group, etc.), aryl group (eg, phenyl group, naphthyl group, etc.), acylamino group (eg, acetylamino group, benzoylamino group, etc.), alkenyl Group (for example, 2-propenyl group, 3-butenyl group, 1-methyl-3-propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, cyclohexenyl group, etc.), heterocyclic ring Groups (for example, pyridyl, thiazolyl, oxazolyl, imidazolyl, etc.), alkoxy groups (for example, metho Si group, ethoxy group, propoxy group etc.), aryloxy group (eg phenoxy group, naphthyloxy group etc.), heterocyclic oxy group, siloxy group, acyloxy group (eg acetyloxy group, benzoyloxy group etc.), amino Group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group, 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (for example, phenylamino group, chlorophenylamino group, toluidino group) , Anisidino group, naphthylamino group, 2-pyridylamino group and the like) and alkoxycarbonylamino groups (for example, methoxycarbonylamino group, phenoxycarbonylamino group and the like).

In the general formula [2], R ₃ is preferably an alkyl group, an aryl group, a heterocyclic group, an amino group, or an anilino group.

In the general formula [2], R ₄ represents a substituent, and the substituent is not particularly limited. For example, an alkyl group (for example, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, pentyl group) Hexyl group, octyl group, dodecyl group etc.), cycloalkyl group (eg cyclopentyl group, cyclohexyl group etc.), aryl group (eg phenyl group, naphthyl group etc.), acylamino group (eg acetylamino group, benzoylamino) Group), alkylthio group (eg, methylthio group, ethylthio group, etc.), arylthio group (eg, phenylthio group, naphthylthio group, etc.), alkenyl group (eg, 2-propenyl group, 3-butenyl group, 1-methyl-3). -Propenyl group, 3-pentenyl group, 1-methyl-3-butenyl group, 4-hexenyl group, Chlorohexenyl group, etc.), halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom etc.), alkynyl group (eg propargyl group etc.), heterocyclic group (eg pyridyl group, thiazolyl group, oxazolyl group, imidazolyl group) Etc.), alkylsulfonyl groups (eg, methylsulfonyl group, ethylsulfonyl group, etc.), arylsulfonyl groups (eg, phenylsulfonyl group, naphthylsulfonyl group, etc.), alkylsulfinyl groups (eg, methylsulfinyl group, etc.), arylsulfinyl groups (For example, phenylsulfinyl group), phosphono group, acyl group (acetyl group, pivaloyl group, benzoyl group, etc.), carbamoyl group (for example, aminocarbonyl group, methylaminocarbonyl group, dimethylaminocarbonyl group, butylaminocarbonyl group, Cyclohexylaminocarbonyl group, phenylaminocarbonyl group, 2-pyridylaminocarbonyl group, etc.), sulfamoyl group (for example, aminosulfonyl group, methylaminosulfonyl group, dimethylaminosulfonyl group, butylaminosulfonyl group, hexylaminosulfonyl group, cyclohexylaminosulfonyl group) Group, octylaminosulfonyl group, dodecylaminosulfonyl group, phenylaminosulfonyl group, naphthylaminosulfonyl group, 2-pyridylaminosulfonyl group, etc.), sulfonamide group (for example, methanesulfonamide group, benzenesulfonamide group, etc.), cyano group , Alkoxy groups (eg, methoxy group, ethoxy group, propoxy group, etc.), aryloxy groups (eg, phenoxy group, naphthyloxy group, etc.), heterocyclic oxy groups, Roxy group, acyloxy group (for example, acetyloxy group, benzoyloxy group, etc.), sulfonic acid group, aminocarbonyloxy group, amino group (for example, amino group, ethylamino group, dimethylamino group, butylamino group, cyclopentylamino group) , 2-ethylhexylamino group, dodecylamino group, etc.), anilino group (eg, phenylamino group, chlorophenylamino group, toluidino group, anisidino group, naphthylamino group, 2-pyridylamino group, etc.), imide group, ureido group (eg, Methylureido group, ethylureido group, pentylureido group, cyclohexylureido group, octylureido group, dodecylureido group, phenylureido group, naphthylureido group, 2-pyridylaminoureido group), alkoxycarbonylamino group (for example, Methoxycarbonylamino group, phenoxycarbonylamino group, etc.), alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl, etc.), aryloxycarbonyl group (eg, phenoxycarbonyl group, etc.), heterocyclic thio group, thioureido And groups such as a group, a carboxyl group, a hydroxyl group, a mercapto group, and a nitro group.

In the general formula [2], X represents an oxygen atom or N—R ₅ , and R ₅ represents a substituent.

Examples of the substituent represented by R ₅ include the same groups as the substituent represented by R _{3 in} the general formula [2].

The substituent represented by R ₅ is preferably an alkyl group, an aryl group, a heterocyclic group, an amino group, or an anilino group.

In general formula [1], at least one of R ₁ or R ₂ and in general formula [2], at least one of R ₃ , R ₄ or R ₅ represents a dye moiety having a chromophore.

  When the main absorption of the dye part is a dye part having a wavelength of 400 to 500 nm, examples of the dye include phenols, naphthols, anilines, pyrazolones, and pyridones as coupling components (hereinafter referred to as coupler components). Aryl or heteryl azo dyes having a heterocycle, an open-chain active methylene compound, etc .; for example, azomethine dyes having an open-chain active methylene compound as a coupler component; for example, benzylidene dyes, monomethine oxonol dyes, etc. Methine dyes; for example, quinone dyes such as naphthoquinone dyes and anthraquinone dyes, and other dye types include quinophthalone dyes, nitro / nitroso dyes, acridine dyes, acridinone dyes, and the like.

  When the main absorption of the dye part is a dye part of 500 to 600 nm, examples of the dye include aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, pyrazolones as coupler components Azomethine dyes having pyrazolotriazoles; methine dyes such as arylidene dyes, styryl dyes, merocyanine dyes, cyanine dyes, oxonol dyes; and the like, such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, etc. Carbonium dyes; for example, quinone dyes such as naphthoquinone, anthraquinone and anthrapyridone; and condensed polycyclic dyes such as dioxazine dyes.

  When the main absorption of the dye part is a dye part having a wavelength of 600 to 700 nm, examples of the dye include aryl or heteryl azo dyes having phenols, naphthols, anilines, etc. as coupler components; for example, phenols as coupler components Azomethine dyes having heterocycles such as naphthols, pyrrolotriazoles, pyrrolopyrazoles, pyrazoloquinazolones; for example, polymethine dyes such as cyanine dyes, oxonol dyes, merocyanine dyes; for example, diphenylmethane dyes, triphenyl And carbonium dyes such as methane dyes and xanthene dyes; phthalocyanine dyes; anthraquinone dyes; indigo / thioindigo dyes.

  Each of the dyes described above may exhibit a color only after part of the chromophore (chromophore) is dissociated, and the counter cation in that case may be an inorganic cation such as an alkali metal or ammonium. In addition, it may be an organic cation such as pyridinium or quaternary ammonium salt, and may further be a polymer cation having them in a partial structure.

  As described above, the dye portion having a chromophore can include various dyes, of which azo dyes, azomethine dyes, methine dyes and quinone dyes are preferred, azo dyes and azomethine dyes are particularly preferred, and color development. Most preferably, the group is represented by the general formulas [3], [4] and [5].

  Hereinafter, the general formula [3] will be described.

L ₁ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent. As an arylene group, Preferably it is C6-C40, More preferably, it is C6-C20, More preferably, it is C6-C12, for example, a phenylene group, a naphthylene group, an anthracenylene group etc. are mentioned, As heteroarylene groups, Preferably it contains an oxygen atom, sulfur atom or nitrogen atom, preferably 1 to 40 carbon atoms, more preferably 2 to 20 carbon atoms, still more preferably 2 to 12 carbon atoms, for example, a pyrazolylene group, a triazolylene group, Examples include a pyridylene group, a thienylene group, a carbazolylene group, and the like. The arylene group or heteroarylene group represented by L ₁ may have a substituent, and examples of the substituent include the same groups as the substituent represented by R ₁ .

In the general formula [3], X ₁ represents a coupler residue. A coupler is a color former and is a compound having an active methylene or active methine group, and is a compound capable of forming a dye by coupling with an active cation radical or diazonium compound which is an oxidant of a color developing agent. Since the color developing agent is oxidatively coupled to the active methylene or active methine group which is an active point of a coupler to form a dye, formally hydrogen from the active point of the active methylene or active methine compound as the coupler. A group in which one or two are removed is a coupler residue.

  The coupler residue is particularly preferably a cyclic compound, specifically 5-pyrazolone, imidazole, pyrazolopyrrole, pyrazoloimidazole, pyrazolotriazole, pyrazolotetrazole, pyrazolopyrimidin-7-one, barbituric acid, thio Examples of the residues include barbituric acid, rhodanine, hydantoin, thiohydantoin, oxazolone, isoxazolone, indandione, pyrazolidinedione, oxazolidinedione, hydroxypyridone, pyrazolopyridone, and cyclohexadienone. More specific examples include the following coupler residues.

  U.S. Pat. Nos. 3,933,501, 4,022,620, 4,326,024, 4,401,752, and 4,248,961, JP-B 58- No. 10739, British Patent Nos. 1,425,020, 1,476,760, U.S. Pat.Nos. 3,973,968, 4,314,023, 4,511,649, European Patents Each specification of No. 249,473A, the coupler represented by the formulas (1) and (2) of the specification of 502,424A, and the formulas (1) and (2) of the specification of 513,496A Couplers (especially Y-28 on page 18), couplers represented by formula (1) of claim 1 of 568,037A, lines 45 to 55 of column 1 of US Pat. No. 5,066,576 A coupler represented by the general formula (1): A coupler represented by the general formula (1) in paragraph 0008 of Kaihei 4-274425, a coupler described in claim 1 on page 40 of EP 498,381A1 (particularly, D-35 on page 18), Couplers represented by formula (Y) on page 4 of 447,969A1 (in particular, Y-1 (page 17), Y-54 (page 41)), U.S. Pat. No. 4,476,219. Couplers (especially II-17, 19 (column 17), II-24 (column 19)) represented by the formulas (2) to (IV) in column 7 to line 36 to 58, and the like. Furthermore, U.S. Pat. Nos. 3,061,432, 3,725,067, 4,310,619, 4,351,897, EP 73,636, U.S. Pat. Nos. 061,432 and 3,725,067, Research Disclosure No. 24220 (June 1984), ibid. 24230 (June 1984), JP-A-60-33552, JP-A-60-43659, JP-A-61-72238, JP-A-60-35730, JP-A-55-118034, JP-A-60-185951, US Patent Nos. 4,500,630, 4,540,654, 4,556,630, International Publication WO88 / 04795 pamphlet, JP-A-3-39737, L-57 (page 11) Lower right), L-68 (page 12, lower right), L-77 (page 13, lower right), [A-4] -63 (page 134), [A-4] of European Patent No. 456,257. ] -73, -75 (page 139), M-4, -6 (page 26), M-7 (page 27) of the specification 486,965, M-45 of the specification 571,959A 19) and (M-1) of JP-A-5-204106. (Page 6), M-22, etc. Paragraph 0237 of the same 4-362631 JP. Furthermore, U.S. Pat. Nos. 4,052,212, 4,146,396, 4,228,233, 4,296,200, 4,146,396, 4,609, 619, 4,775,616, 4,849,328, 5,008,180, 5,045,442, 5,183,729, European Patent 73,636 , CX-1, 3, 4, 5, 11, 12, 14, 15 (pages 14 to 16) of JP-A-4-204843; C-7, 10 of JP-A-4-43345 (Page 35), 34, 35 (page 37), (I-1), (I-17) (pages 42-43); JP-A-6-67385, claim 1 general formula (Ia) or ( Examples thereof include couplers represented by Ib). In addition, JP-A-62-215272 (page 91), JP-A-2-33144 (pages 3, 30), and European Patent No. 355,660A (pages 4, 5, 45) , P. 47) are also useful.

In the general formula [4], L ₂ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent. Specific examples thereof are the same as those of L ₁ in the general formula [3].

In the general formula [4], R ₇ represents a substituent, and examples of the substituent include the same groups as the substituent represented by R ₁ .

In the general formula [4], Y represents an oxygen atom, ═CR ₈ R ₉ — or ═NR ₁₀ —, R ₈ , R ₉ , R ₁₀ each represents a hydrogen atom or a substituent, and the substituent includes the above R 1 The same group as the substituent represented by can be mentioned. R ₇ , R ₈ , R ₉ and R ₁₀ may be bonded to each other to form a ring.

In the general formula [5], L ₃ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent. Specific examples thereof are the same as those of L ₁ in the general formula [3].

In the general formula [5], X ₂ represents a coupler residue, and specific examples thereof include specific examples similar to X ₁ in the general formula [3].

In the general formula [5], Z represents —N═ or —CR ₁₁ ═, and R ₁₁ represents a hydrogen atom or a substituent. Specific examples of these substituents include the same specific examples as those for R ₁ .

  Specific examples of the compound represented by the general formula [1] are shown below, but the present invention is not limited thereto.

  The dye represented by the general formula [1] may be either water-soluble or oil-soluble, but in the case of oil-solubility, those dispersed in an aqueous medium are preferable. The aqueous medium only needs to contain at least water. Specifically, water or a mixture of water and a water-miscible organic solvent, if necessary, a surfactant and an anti-drying agent (wetting agent). Preferred are those added with additives such as stabilizers and preservatives.

  In the present invention, when a plurality of dyes are contained, each dye may or may not be the same amount, and the mixture amount so as to form black by mixing according to the color tone of each dye. Is appropriately changed.

  The colored composition (black composition) of the present invention contains at least the dye of the present invention as described in the above claims, and may further contain any other dye to form a black color. Selection of a preferred dye is easy for those skilled in the art.

  Examples of carbon black used in the present invention include No. 1 manufactured by Mitsubishi Chemical. 2300, no. 900, MCF88, No. 33, no. 40, no. 45, no. 52, MA7, MA8, MA100, no. 2200B, etc. are Raven5750, Raven5250, Raven5000, Raven5000, Raven3500, Raven1255, Raven700, etc. manufactured by Columbia, and Regal 400R, Regal 330R, Regal 660R, Mulch 800, Monar 800, Monch 800, Monch 800, manufactured by Cabot. Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, etc. are available from Degussa Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color BlackColF black S160, Color Black S170, Printex 35, Printex U, Printex V, Printex 140U, Special Black 6, Special Black 5, Special Black 4A, Special 4 can be used.

  The dye used in the present invention is not particularly limited, and known acid dyes, direct dyes, reactive water-soluble dyes such as reactive dyes, and oil-soluble dyes that are conventionally used can be used.

  Examples of the dye include C.I. I. Acid Yellow 17, 23, 42, 44, 79, 142; I. Acid Red 1, 8, 13, 14, 18, 26, 27, 35, 37, 42, 52, 87, 89, 92, 97, 106, 111, 114, 115, 186, 249, 254, 289; I. Acid Blue 9, 29, 45, 92, 249; I. Acid Black 1, 2, 7, 24, 26, 94; I. Direct yellow 1, 12, 24, 26, 33, 44, 50, 86, 120, 132, 142, 144; I. Direct red 1, 4, 9, 13, 17, 20, 28, 31, 39, 80, 81, 83, 89, 225, 227; I. Direct Blue 1, 2, 6, 15, 22, 25, 71, 76, 79, 86, 87, 90, 98, 163, 165, 199, 202; C.I. I. Direct black 19, 22, 32, 38, 51, 56, 71, 74, 75, 77, 154, 168, 171; I. Basic Yellow 1, 2, 11, 13, 14, 15, 19, 21, 23, 24, 25, 28, 29, 32, 36, 40, 41, 45, 49, 53, 63, 64, 65, 67, 70, 73, 77, 87, 91; C.I. I. Basic Red 2, 12, 13, 14, 15, 18, 22, 23, 24, 27, 29, 35, 36, 38, 39, 46, 49, 51, 52, 68, 70, 73, 78, 82, 102, 104, 109, 112; C.I. I. Basic Blue 1, 3, 5, 7, 9, 21, 22, 26, 35, 41, 45, 47, 54, 62, 65, 66, 67, 69, 75, 77, 89, 92, 93, 105, 117, 120, 122, 124, 129, 137, 141, 155; I. B. Basic Black 2, 8; I. Reactive yellow 1, 5, 11, 13, 14, 20, 21, 22, 25, 40, 47, 51, 55, 65, 67; C.I. I. Reactive Red 1, 14, 17, 25, 26, 32, 37, 44, 46, 55, 60, 66, 74, 79, 96, 97; C.I. I. Reactive blue 1, 2, 7, 14, 15, 23, 32, 35, 38, 41, 63, 80, 95; I. Reactive Black 3, 4, 7, 11, 12, 17, C.I. I. Solvent yellow 1, 2, 3, 13, 19, 22, 29, 36, 37, 38, 39, 40, 43, 44, 45, 47, 62, 63, 71, 76, 81, 85, 86, etc. C. I. Solvent Red 8, 27, 35, 36, 37, 38, 39, 40, 58, 60, 65, 69, 81, 86, 89, 91, 92, 97, 99, 100, 109, 118, 119 and 122 etc. . C. I. Solvent Blue 14, 24, 26, 34, 37, 38, 39, 42, 43, 45, 48, 52, 53, 55, 59 and 67 etc. C. I. Solvent black 3, 5, 7, 8, 14, 17, 19, 20, 22, 24, 26, 27, 28, 29, 43, and 45 are used.

  The content of the compound represented by the general formula [1] in the inkjet recording liquid is preferably in the range of 0.1 to 25% by mass, more preferably in the range of 0.5 to 10% by mass.

  The ink jet recording liquid of the present invention having the compound of the general formula [1] can use various solvent systems such as an aqueous solvent, an oil solvent, a solid (phase change) solvent, etc., and the effects described in the present invention. From the viewpoint of preferably obtaining the above, it is particularly preferable to use an aqueous solvent as described below.

《Aqueous solvent》
As the aqueous solvent, a mixed system of water (for example, ion-exchanged water is preferable) and a water-soluble organic solvent is preferably used.

  Examples of water-soluble organic solvents include alcohols (eg, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, secondary butanol, tertiary butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol, etc.), polyhydric alcohols (For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, etc.), polyhydric alcohol ether (E.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethyl Glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl Ether, propylene glycol monophenyl ether, etc.), amines (for example, ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenediamine, triethylamine) Tylenetetramine, tetraethylenepentamine, polyethyleneimine, pentamethyldiethylenetriamine, tetramethylpropylenediamine, etc.), amides (eg, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, etc.), heterocycles (eg, 2-pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, etc.), sulfoxides (eg dimethyl sulfoxide etc.), sulfones (eg sulfolane) Etc.), urea, acetonitrile, acetone and the like.

  Among the above water-soluble organic solvents, polyhydric alcohols are particularly preferably used.

  The aqueous solvent can be used as it is if the compound represented by the general formula [1] is soluble in the solvent system. In this case, the solubility of the compound represented by the general formula [1] in an aqueous solvent is important, and structural features of the compound include a sulfo group or a salt thereof (for example, sodium salt, potassium salt, etc. Of at least one alkali metal salt, 1/2 calcium salt, ammonium salt, etc., more preferably at least two.

<< Fine particle dispersion (also called colored particle dispersion) >>
The fine particle dispersion of the compound represented by the general formula [1] according to the present invention will be described.

  The compound represented by the general formula [1] is substantially insoluble in the above aqueous solvent in the state of the compound alone (here, substantially insoluble means that the solubility in the aqueous solvent is 0.1 mass). % Of the compound in the form of various dispersers (eg, ball mill, sand mill, attritor, roll mill, agitator mill, Henschel mixer, colloid mill, ultrasonic homogenizer, pearl mill, After the compound is dissolved in a soluble organic solvent, it is dispersed in a solvent system that is insoluble in the state of the compound alone with the polymer dispersant or surfactant. be able to.

  Alternatively, the compound is kneaded with a resin (also referred to as a polymer) and then dispersed in an aqueous system to prepare a colored fine particle dispersion in a state where the compound is coated with the resin, or a solution obtained by dissolving the resin in an organic solvent is used as the compound And a method of preparing a colored fine particle dispersion by removing the solvent under reduced pressure and coating with a resin.

  Furthermore, when the solvent system is a solid medium or a semi-molten material or the like (in the case of a material such as a wax described later) at room temperature or the like, the solid state remains as the semi-molten material or those Can be dissolved in a soluble organic solvent and dispersed in the solvent system together with a polymer dispersant or a surfactant.

  The fine particle dispersion according to the present invention contains fine particles containing at least one kind of the compound represented by the general formula [1] and a resin as constituent components, and the fine particle dispersion has a core / shell structure. It is preferable to contain fine particles.

  The colored fine particle dispersion preferable in the present invention will be described in detail later. From the viewpoint of improving the stability of the colored fine particle as an aqueous dispersion and preferably improving the fastness of the dye and the effect of improving the color tone, the surface of the fine particle The surface layer is preferably composed of a relatively hydrophilic resin.

  In addition, the dispersion of the colored fine particle dispersion is prevented for a longer period of time, the stability of the fine particle as an ink suspension is improved, and the color tone and gloss of the image when printed on a medium, light resistance, and the like are robust to the image. In order to impart the property, it is preferable to form a shell portion made of an organic polymer (oil-soluble and water-dispersible polymer) with colored fine particles (resin dispersed particles containing a pigment) as a core portion. .

(Colored fine particles having a core / shell structure)
When the fine particles constituting the fine particle dispersion according to the present invention form a core / shell structure, the configurations of the core portion and the shell portion include the following combinations.

Core part Shell part (1) Dye Resin (2) Dye + Resin Resin Among the above combinations, from the viewpoint of improving the dispersion stability of the core / shell particles, the core part contains a resin and a dye, and the shell part is made of resin. Preferred combination (2) is preferred.

(Ratio of resin forming core / shell)
From the viewpoint of improving the stability of the core-shell structure (preventing a part of the core from appearing on the particle surface and improving the pigment protecting property of the core part), the amount of resin used in the shell is 5 to 95 of the total resin amount. It is preferable that it is the range of the mass%, More preferably, it is 10-90 mass%.

(Dye to resin ratio)
From the standpoint of adequately maintaining the image density after ink ejection and sufficiently functioning the protective ability of the resin against the pigment, the mass of the pigment is preferably in the range of 20 to 1000% by mass with respect to the total amount of resin.

(Particle size of fine particles)
In the present invention, when the compound represented by the general formula [1] (also referred to as a pigment) is insoluble in an aqueous solvent system and dispersed in the form of fine particles, the particle size of the fine particles (colored fine particles) in the fine particle dispersion Is more preferably dispersed so that the average particle size is 150 nm or less.

  In addition, at least one of the compounds represented by the general formula [1] is surely enclosed in the core-shell resin, and the ease of clogging of the head when the obtained fine particle dispersion is used as an ink is reduced. From the viewpoint of preventing sedimentation of the fine particle dispersion in the ink jet recording liquid and improving the storage stability of the ink jet recording liquid (also referred to as stagnation stability, stability over time, etc.), the volume average of the core / shell fine particles The particle diameter is preferably adjusted in the range of 1 to 200 nm, more preferably in the range of 3 to 100 nm.

(Volume average particle diameter)
Here, the volume average particle diameter of the fine particles is obtained by converting the circular average particle diameter obtained from the average value of the projected area (determined for at least 100 particles) of the transmission electron microscope (TEM) photograph into a spherical shape. Desired. The coefficient of variation can be obtained by determining the volume average particle size and its standard deviation and dividing the standard deviation by the volume average particle size. Alternatively, the coefficient of variation can be obtained using a dynamic light scattering method. For example, it can be determined using a laser particle size analysis system manufactured by Otsuka Electronics or a Zetasizer manufactured by Malvern.

(Particle diameter variation coefficient)
The variation coefficient of the particle diameter is a value obtained by dividing the standard deviation of the particle diameter by the particle diameter, and the larger this value is, the wider the distribution of the particle diameter is.

  Improves core shell thickness uniformity, uniforms the surface physical properties between particles, reduces particle agglomeration, prevents clogging of inkjet heads, prevents unnecessary light scattering of dye on media, and improves image quality From the viewpoint of obtaining the effect of suppressing the decrease, the variation coefficient of the particle diameter is preferably less than 80%, more preferably 50% or less, and particularly preferably 30% or less.

<Method for forming core-shell structure>
Examples of the fine particles having a core / shell structure according to the present invention include a method in which a resin core containing the pigment according to the present invention is first prepared, and then a method in which a resin shell is provided and a method in which a core and a shell are simultaneously provided.

(A) Method for Providing Shell after Fabrication of Fine Particle Core The dye-containing (also referred to as dye-containing) resin that becomes the core can be prepared by various methods. For example, there is a technique in which a pigment and a resin are kneaded and then dispersed in an aqueous system to prepare a resin-coated pigment. As a method of providing a resin shell, a method of adding a water-soluble resin dispersant to an aqueous suspension of a resin as a core and adsorbing it, a method of gradually dropping a monomer and depositing it on the core surface simultaneously with polymerization, or an organic solvent There is a method in which a resin dissolved in is gradually dropped and adsorbed on the core surface simultaneously with precipitation.

  In the present invention, a method in which a monomer is gradually dropped onto an aqueous suspension of a resin serving as a core and deposited on the core surface simultaneously with polymerization is particularly preferable.

(B) A method in which a core and a shell are provided at the time of forming fine particles. A method in which a core resin and a dye are dissolved or dispersed in a monomer to be a shell after polymerization, suspended in water and polymerized, There is also a technique of emulsion polymerization while gradually dropping into the contained water. The monomer may be a core and the resin may be a shell. Alternatively, there is a technique in which a dye is dissolved or dispersed in a monomer mixed solution that can become a core and a shell after polymerization, and suspension polymerization or emulsion polymerization is performed.

(Evaluation method of core-shell structure)
It is important to evaluate whether the colored fine particles are actually core-shelled. In the present invention, as will be described later, since the individual particle diameter of the colored fine particles is as very small as 200 nm or less, the analysis method is limited from the viewpoint of resolution.

  As an analysis method meeting such a purpose, TEM (transmission electron microscope), TOF-SIMS (time-of-flight secondary ion mass spectrometry), or the like can be applied. When observing fine particles that have been core-shelled by TEM, the dispersion can be applied on a carbon support film, dried and observed. The TEM observation image shows that the contrast difference may be small if only the type of resin that is an organic substance is used. Therefore, in order to evaluate whether or not the core shell is formed, the fine particles are made of osmium tetroxide, ruthenium tetroxide, chlorosulfonic acid / acetic acid. It is preferable to dye using uranyl, silver sulfide or the like.

  Dye the fine particles of the core only, observe the TEM, and compare with the one provided with the shell. Further, after mixing the fine particles provided with the shell and the fine particles not provided with the shell, the particles are dyed, and it is confirmed whether the proportion of the fine particles having different dyeing degree matches the presence or absence of the shell.

  In a mass spectrometer such as TOF-SIMS, it is confirmed that by providing a shell on the particle surface, the amount of dye near the surface is reduced as compared with the case of only the core. When there is an element that is not contained in the core-shell resin in the dye, it can be confirmed whether or not a shell having a low dye content is provided using the element as a probe.

  In other words, the dye content (concentration) is measured by measuring the total amount of ions in the mass range of 1 to 1,000 on the surface of each fine particle using TOF-SIMS. A ratio with the total amount of ions derived from elements not contained in the resin is calculated. Then, the dye content (concentration) can be measured by comparing this method with the shell, the core not subjected to core / shell formation, and the dye content of each core.

  Since TOF-SIMS can perform elemental analysis of several nm in the depth direction from the surface, analysis of core / shell fine particles is possible.

  Even in the absence of the specific element as described above, the dye content in the shell can be compared with that of the particles not provided with the shell by using an appropriate staining agent.

  Moreover, core-shell formation can be observed more clearly by embedding the core-shell particles in an epoxy resin, preparing an ultrathin section with a microtome, and performing staining. As described above, when the resin or the dye contains an element that can be a probe, the composition of the core shell and the distribution amount of the dye to the core and the shell can be estimated by TOF-SIMS or TEM.

<< Preferred physical properties of resin for forming colored fine particle dispersion >>
The physical properties required for the resin for forming the colored fine particle dispersion are, of course, high compatibility and affinity with any one compound (pigment) of the general formulas [1] and [2], Strong interaction for improving color tone and storage stability, moderate hydrophobicity for maintaining the dispersion system, and moderate hydrophilicity for improving dispersion stability at the same time. Various properties such as a high glass transition point (Tg) (however, a low Tg is better for improving dispersion stability) are required to improve the properties.

  Conventionally, in composite resin particles that have been used together with coloring materials such as dyes and pigments, it is preferable to use, for example, a resin having high compatibility or affinity with dyes and pigments in order to obtain colored fine particles having good color tone.

  In the present invention, as means for controlling the physical properties required of the resin for forming the colored fine particle dispersion, attention was paid to the log P (hydrophobic and hydrophilic parameters) and the solubility parameter of the resin as shown below.

<< LogP: Hydrophobic and hydrophilic parameters >>
The present inventors have optimized various properties required for colored fine particles and fine particle dispersions used in ink, and in order to achieve each of them in a high degree, a single resin or a plurality of different resins are used. Basically, by distributing these resin components inside and outside according to the respective properties, for example, the physical strength of the colored fine particles is increased, that is, the adhesion stability between the core portion and the shell portion is improved. While simultaneously improving the dispersion stability of the colored fine particles in the ink medium, and further improving the color tone and the light resistance of the ink, it is possible to simultaneously control various requirements that have been trade-offs in the past 1 As one means, attention was focused on the relative relationship between the resin contained in the core of the core-shell particle and the resin contained in the shell with LogP.

(Resin contained in the core, resin contained in the shell)
In preparation of colored fine particles having a core / shell structure according to the present invention, it is important to optimize the formulation and select an appropriate emulsification method in order to prepare a preferable dispersed particle size. The formulation varies depending on the dye and resin used, but since it is a suspension in water, it is generally preferable that the resin constituting the core is more hydrophilic than the resin constituting the core. Moreover, it is preferable that the pigment | dye contained in resin which comprises a shell is less than the resin which comprises a core as mentioned above.

  In the present invention, as a means for adjusting the hydrophobicity and hydrophilicity of the core part and the shell part, there is control using the LogP value. That is, since a resin with a low LogP value has a high affinity for water, in the colored fine particle dispersion according to the present invention, it is used in a site close to the outside of the particle. Since the higher the property, the more preferable the pigment can be coated, it is preferable to use a material having high hydrophobicity.

  However, if the difference between the Log P1 of the core resin and the Log P2 of the shell resin is too large, the adhesiveness at the core / shell interface tends to be reduced, and the physical strength of the colored fine particles is reduced and the dispersion stability is reduced. Therefore, | LogP1-LogP2 | is preferably 4 or less.

  Therefore, as a combination of a resin having a high coating effect and dispersion stability, for example, a resin such as polyvinyl butyral is provided on the outer side (shell layer) and has a log P value larger than that of polyvinyl butyral. It is preferable to distribute a resin having high affinity with at least one compound represented by

  The Log P value is a parameter that represents a measure of the hydrophilicity-hydrophobicity of a material. The larger the value, the more hydrophobic it is, and the smaller the value, the more hydrophilic it is. The LogP value is a widely known parameter of a compound, and can be measured by an ordinary method, or an approximate value can be obtained by calculation.

  In the present invention, the difference in Log P value between the resin used for the core part and the resin used for the shell part is preferably 4.0 or less, and more preferably 3.5 or less.

  Different types of resins have structurally different parts and have different macromolecular or micro level interactions with pigment molecules and dye molecules, or different molecular weights, and thermodynamics. Which are considered to differ in terms of general properties and the level of interaction with dye molecules or between resin components.

  Therefore, even in the same resin, a partly modified one, a copolymer having a different composition ratio of each monomer component, and a monomer unit (which may be a copolymer) are structural. Even if they are the same, the molecular weight distribution is clearly different. For example, resins having different softening points, melting points, thermodynamic properties such as solubility, and chemical affinity are different. it is conceivable that.

  The core-shell microparticles according to the present invention are characterized in that they are used even if they are mixed with slightly different resins, and the effects of the present invention cannot be obtained by mixing those having very close properties.

  In addition, as will be described later, the calculated LogP value does not completely match the partition coefficient that can be defined by the following equation of the substance in the two solvent systems to n-octanol and water, In some cases, there may be a slight difference. Actually, different resins that have different micro or macro properties may have the same value, and it is not accurate for LogP. When viewed, approximately 0.1 is preferable.

  Here, LogP is a parameter representing hydrophobicity / hydrophilicity, and can be obtained from a partition coefficient that can be defined by the following equation of a substance in two solvent systems, usually n-octanol and water.

LogPo / w, Po / w = So / Sw
So: Solubility of the organic compound in n-octanol at 25 ° C. Sw: Solubility of the organic compound in pure water at 25 ° C. These are the chemical domain extra number 122 “Structure-activity relationship of drugs” (Nanedo) 73- It is described in detail on page 103. In recent years, methods for obtaining LogP by calculation have been proposed, and those based on molecular orbital calculations or basically C.I. There are a fragment method using Hansch data and a method by HPLC.

  The LogP calculation program used in the present invention is Project Leader in a molecular calculation package called CAChe from Fujitsu Limited. K. Ghost, et al, J.A. Comput. Chem. 9:80 (1988).

<< Solubility parameter >>
The solubility parameter, which is one of the parameters useful for controlling the physical properties required for the resin for forming the colored fine particle dispersion of the present invention, will be described.

When producing colored fine particles, the affinity between the dye and the resin in the core is improved, and the affinity between the core and the shell containing the dye and the resin is improved. The solubility parameter (SP value) of the resin according to the present invention is preferably 3 (MPa) ^1/2 to 30 (MPa) ^1/2 , more preferably 5 (MPa) ^{1 / 2 to} 20 (MPa) ^1/2 , particularly preferably 7 (MPa) ^1/2 to 15 (MPa) ^1/2 .

  The solubility parameter according to the present invention will be described.

  The solubility parameter is a value obtained from the solubility parameter of Hildebrand, which is often used when evaluating the ease of dissolution of the non-electrolyte in an organic solvent. This solubility parameter is described in J. Org. H. Hildebrand, J.M. M.M. Prausnitz. R. L. See “Regular and Related Solutions” by Scott, Van Nostrand-Reinhold, Princeton (1970), “Polymer Data Handbook Fundamentals”, Polymer Society. The solubility parameter values of various solvents are as follows. F. M.M. Barton, “Handbook of Solrity Parameters and Other Cohesion Parameters”, CRC Press, Boca Raton / Florida (1983), “Polymer Data Handbook Fundamentals”, Polymer Society.

The solubility parameter of the substance is defined as SP = (δE / V) ^1/2 , where δE is the cohesive energy per mole and V is the molar volume.

  The solubility parameter can be determined by several methods, such as a method for determining from solubility, or a latent heat of vaporization method, a vapor pressure method, a swelling method, a surface tension method, a thermal swelling coefficient method, and a refractive index method.

In the present invention, any solubility parameter determined by the following method is used. The unit is represented by (MPa) ^1/2 in the present invention.

  The solubility parameter can be determined from the solubility of various SP values in known solvents. This method for determining the solubility parameter based on the solubility in a solvent is effective when the structure of the dye or the like is unknown.

  In the pigment of the present invention, for example, various solvents with known SP values such as ethanol, acetone, methyl ethyl ketone, ethyl acetate, etc. are used, and a dissolution method for obtaining the SP value of a dye as a solute from the SP value of the solvent having the highest solubility is used. Use. In this method, δd (dispersion force term), δp (polarity term), and δh (hydrogen bond term), which are the components of the SP value of each solvent of the highest solubility group, are plotted separately for each term, Find the center value for each term. As the value of each term of the SP value of the dye, the SP value of the dye can be determined by using this central value (CM Hansen, J. Paint Technol., 39 (505) 104 (1967), C M. Hansen, J. Paint Technol., 39 (511) 505 (1967)).

  Although it is difficult to accurately obtain the SP value by a dissolution method with a dye having low solvent solubility, the above-mentioned document shows measurement using a suspended state. That is, a solvent having a closer SP value wets the dye better. Therefore, after mixing the solvent and the dye, shake well and a good suspended (non-settling) solvent can be used, such as ethanol, acetone, methyl ethyl ketone, and ethyl acetate. The solvent is selected from a plurality of solvents (may be plural), and δd (dispersion force term), δp (polarity term), and δh (hydrogen bond term) of each solvent in a good suspension state are divided for each term. Plot, calculate the center value of each δd (dispersion force term), δp (polarity term), and δh (hydrogen bond term), respectively, and calculate the center value of each calculated term as each term of the SP value of the dye. Thus, the SP value of the dye can be obtained.

  The solubility parameter can be obtained by calculation when the structure is known.

  Small related chemical composition and SP value, and proposed a calculation method in which SP value is obtained by dividing the sum of molar attractive constants ΔF in a molecule by molar volume V. In this method, ΔF can be easily calculated because it can be assigned to each atomic group.

S = (ΣΔF) / V
However, since the Small equation includes only the cohesive energy generated from the dispersion force, Rheineck, Hoy, Krebelen, and Fedors have proposed different modified ΔFs in order to further improve the accuracy of the above calculation method. Hansen also proposed three-dimensional decomposed parameters. The numerical value varies slightly depending on each correction parameter, but the error when viewed as the difference between the two types of dyes defined in the present invention is small. When the structure is known, the solubility parameter obtained by the calculation using the correction parameter can be used. The calculation program used in the present invention is Project Leader in a molecular calculation package called CAChe manufactured by Fujitsu Limited.

  The solubility parameter calculated by any of these methods is used in the present invention. For example, when the solubility parameter value is determined from the solubility in the solvent, the solubility parameter value of the solvent to be used may be slightly different depending on the method to be obtained, and the SP value of the dye is slightly different accordingly. . However, since the difference in the values is not so large, the SP value difference between the dyes may be the one with the smallest difference.

Therefore, in the case of a dye or pigment having a known structure, it is preferable to use the calculation method described above. If the difference between the solubility parameters of the two or more dyes thus determined is within 4.0 (MPa) ^1/2 , the dyes have an appropriate affinity and only one dye is used. This is preferable because the affinity with the resin does not decrease due to the strength of the cohesive force between the molecules, and the compatibility with the resin is improved.

  Incidentally, the specific numerical values of the solubility parameter according to the present invention are, in principle, those described in J. Org. BRANDRUP and E. H. Numerical values described in IMMERGUT, “POLYMER HANDBOOK”, THIRD EDITION, JOHN WILEY & SONS (1989) were used. However, the numerical value calculated | required by calculation (simulation) was used about the thing which is not described in the said literature.

  Further, from the viewpoint of improving the film-forming property after printing, its durability and the formability of the suspension, the resin used in the core preferably has a number average molecular weight in the range of 500 to 100,000, particularly preferably 1. , 30,000 to 30,000. Various Tg of the resin can be used, but it is preferable to use at least one of the resins to be used having a Tg of 10 ° C. or more.

  In the present invention, all generally known resins can be used, but particularly preferable resins include resins containing an acetal group as a main functional group, resins containing a carbonate group, and resins containing a hydroxyl group. And a resin having an ester group. The above resin may have a substituent, and the substituent may have a linear, branched, or cyclic structure. Various resins having the above functional groups are commercially available, but can be synthesized by a conventional method. These copolymers can also be obtained, for example, by introducing an epoxy group into one resin molecule and later performing polycondensation with another resin or graft polymerization using light or radiation.

  In the colored fine particle dispersion according to the present invention, the resin core mainly contains a dye and contributes to maintaining its fastness and color tone, while the resin shell has a stability as an ink suspension of fine particles containing the dye. In addition, it promotes the fixing of dyes on the media, prevents aggregation, and contributes to the improvement of image quality. It also contributes to dye fastness and color tone retention.

  The dye content (concentration) can be measured with a mass spectrometer such as TOF-SIMS as described above. First, the total amount of ions having a mass number of 1 to 1000 is measured on each fine particle surface. The pigment content can be determined from the total amount of ions attributed to the dye. The pigment content of the shell and the core not subjected to core / shell formation are compared. Since TOF-SIMS can perform elemental analysis of several nanometers in the depth direction from the surface, core / shell fine particles as in the present invention can be analyzed.

  In the fine particles having the core / shell form according to the present invention, the ability to protect the dye is appropriate, the maintenance stability as a suspension ink is improved, and the increase in the viscosity of the ink accompanying ink evaporation at the tip of the inkjet nozzle is prevented. From the viewpoint of preventing clogging of the printer head due to suspension agglomeration, the resin amount is preferably 0.5 to 50% by mass, more preferably 0.5 to 30% by mass in the aqueous ink of the present invention. Is Rukoto.

<< Oil-soluble polymer (also called lipophilic polymer) >>
In the inkjet recording liquid of the present invention, from the viewpoint of improving the temporal stability in an ink using an aqueous medium of a fine particle dispersion (colored particle dispersion), the fine particle dispersion contains the compound and an oil-soluble polymer (lipophilic). Polymer).

  Here, the oil-soluble polymer (lipophilic polymer) preferably has a solubility in pure water of 10% by mass or less at room temperature (under atmospheric pressure).

  In preparing the fine particle dispersion using the oil-soluble polymer, the use forms of the oil-soluble polymer include the following forms (c) and (d).

(C) When the fine particle dispersion according to the present invention is prepared in a state where the compound is impregnated in a resin (polymer). (D) The fine particle dispersion according to the present invention has a core region (resin and dye). And a dispersion of core-shell particles consisting of a shell region (including a resin) formed so as to cover the core region. As a preferable example of the embodiment (c), the general formula [1 ] Is dissolved in a soluble organic solvent (also referred to as a lipophilic solvent), and then a fine particle dispersion is prepared together with an oil-soluble polymer (also referred to as a lipophilic polymer) and dispersed in an aqueous solvent. Etc.

  Next, as a preferred example of the embodiment (d), the compound represented by the general formula [1] is dissolved in a soluble organic solvent (also referred to as a lipophilic solvent), and then an oil-soluble polymer ( For example, a core particle (containing an oil-soluble polymer and a pigment as constituents) is prepared, and the core particle is coated with an oil-soluble polymer to form a shell region.

  Also, in the preparation of the fine particle dispersion of either aspect (c) or (d), examples of the method for dispersing the fine particles in the aqueous solvent include, for example, JP-A Nos. 5-148436 and 5-29512. Reference can be made to the methods described in JP-A-7-97541, JP-A-7-82515, JP-A-7-118584, and the like.

  The oil-soluble polymer according to the present invention is not particularly limited and may be appropriately selected depending on the intended purpose. Any conventionally known water-insoluble type, water-dispersed (self-emulsifying) type or water-soluble type polymer is used. Among them, as the oil-soluble polymer forming the shell region used for the preparation of the fine particle dispersion of the aspect (c) and the fine particle dispersion of the aspect (d), the production of colored fine particles can be used. The following water-dispersed polymers are preferably used in terms of ease and dispersion stability.

《Water-dispersed polymer》
The water-dispersed polymer may be either an ion dissociation type, a non-ionic dispersible group-containing type, or a mixture thereof. Examples of the ion dissociation type polymer include a polymer containing a cationic dissociable group such as a tertiary amino group, and a polymer containing an anionic dissociative group such as carboxylic acid and sulfonic acid. Examples of the nonionic dispersible group-containing polymer include polymers containing a nonionic dispersible group such as a polyethyleneoxy chain.

  Among these, from the viewpoint of the dispersion stability of the colored fine particles, an ion dissociation type polymer containing an anionic dissociable group, a nonionic dispersible group containing type polymer, and a mixed type polymer are preferable.

  Examples of the monomer (also referred to as monomer) used for forming the water-dispersed polymer according to the present invention include the following.

That is, acrylic esters, specifically, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chloro Cyclohexyl acrylate, cyclohexyl acrylate, furfuryl acrylate, tetrahi Rofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-butoxyethyl acrylate, 2- (2-methoxyethoxy) ethyl acrylate, 2- (2-butoxyethoxy) ethyl acrylate, glycidyl acrylate, 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, 2,2 , 2-tetrafluoroethyl acrylate, 1H, 1H, 2H, 2H-perfluorodecyl acrylate, etc .;
Methacrylic acid esters, specifically, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate , Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, 2- (3-phenylpropyloxy) ethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate 4-Hido Xylbutyl methacrylate, triethylene glycol monomethacrylate, dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-ethoxyethyl methacrylate, 2-iso-propoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2- (2-methoxyethoxy) ethyl methacrylate, 2- (2-ethoxyethoxy) ethyl methacrylate, 2- (2-butoxyethoxy) ethyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2,2,2-tetrafluoroethyl methacrylate, 1H, 1H, 2H, 2H-perfluorodecyl methacrylate Over doors and the like;
Vinyl esters, specifically vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxy acetate, vinyl vinyl phenyl acetate, vinyl benzoate, vinyl salicylate etc;
Acrylamides, specifically, acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, butyl acrylamide, tert-butyl acrylamide, tert-octyl acrylamide, cyclohexyl acrylamide, benzyl acrylamide, hydroxymethyl acrylamide, methoxymethyl acrylamide, butoxymethyl acrylamide, Methoxyethyl acrylamide, phenyl acrylamide, dimethyl acrylamide, diethyl acrylamide, β-cyanoethyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, diacetone acrylamide, etc .; methacrylamides, specifically, methacrylamide, methyl methacrylamide, Ethyl methacrylamide, propyl Tacrylamide, butylmethacrylamide, tert-butylmethacrylamide, cyclohexylmethacrylamide, benzylmethacrylamide, hydroxymethylmethacrylamide, methoxyethylmethacrylamide, phenylmethacrylamide, dimethylmethacrylamide, β-cyanoethylmethacrylamide, N- (2-acetamide Acetoxyethyl) methacrylamide, etc .; olefins, specifically, dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, etc. ;
Styrenes such as styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, chloromethyl styrene, methoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester, etc .;
Vinyl ethers, specifically methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, etc .;
Other monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl Vinyl ketone, methoxyethyl vinyl ketone, N-vinyl oxazolidone, N-vinyl pyrrolidone, vinylidene chloride, methylenemalonnitrile, vinylidene, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, dibutyl-2-acryloyl Oxyethyl phosphate, dioctyl-2-methacryloyloxyethyl phosphate, and the like.

  Examples of the monomer having a dissociable group include a monomer having an anionic dissociable group and a monomer having a cationic dissociable group.

  Examples of the monomer having an anionic dissociable group include a carboxylic acid monomer, a sulfonic acid monomer, and a phosphoric acid monomer.

  Examples of the carboxylic acid monomer include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, crotonic acid, itaconic acid monoalkyl ester (for example, itaconic acid monomethyl, itaconic acid monoethyl, itaconic acid monobutyl, etc.) And maleic acid monoalkyl esters (for example, monomethyl maleate, monoethyl maleate, monobutyl maleate, etc.).

  Examples of the sulfonic acid monomer include styrene sulfonic acid, vinyl sulfonic acid, acryloyloxyalkyl sulfonic acid (for example, acryloyloxymethyl sulfonic acid, acryloyloxyethyl sulfonic acid, acryloyloxypropyl sulfonic acid, etc.), methacryloyloxyalkyl sulfonic acid ( For example, methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid, methacryloyloxypropylsulfonic acid, etc.), acrylamide alkylsulfonic acid (for example, 2-acrylamido-2-methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid) , 2-acrylamido-2-methylbutanesulfonic acid, etc.), methacrylamide alkylsulfonic acid (for example, 2-methacrylamido- - methyl ethanesulfonic acid, 2-methacrylamide-2-methylpropanesulfonic acid, 2-methacrylamide-2-methylbutanesulfonic acid).

  Examples of the phosphoric acid monomer include vinyl phosphonic acid and methacryloyloxyethyl phosphonic acid.

  Among these, acrylic acid, methacrylic acid, styrene sulfonic acid, vinyl sulfonic acid, acrylamide alkyl sulfonic acid, and methacrylamide alkyl sulfonic acid are preferable, and acrylic acid, methacrylic acid, styrene sulfonic acid, and 2-acrylamide-2 are more preferable. -Methylpropanesulfonic acid, 2-acrylamido-2-methylbutanesulfonic acid and the like.

  Examples of the monomer having a cationic dissociable group include monomers having a tertiary amino group such as dialkylaminoethyl methacrylate and dialkylaminoethyl atacrylate.

  Examples of the monomer containing a nonionic dispersible group include an ester of polyethylene glycol monoalkyl ether and a carboxylic acid monomer, an ester of polyethylene glycol monoalkyl ether and a sulfonic acid monomer, polyethylene glycol monoalkyl ether and phosphorus. Examples thereof include an ester with an acid monomer, a vinyl group-containing urethane formed from a polyethylene glycol monoalkyl ether and an isocyanate group-containing monomer, and a macromonomer containing a polyvinyl alcohol structure. As a repeating number of the ethyleneoxy part of the said polyethylene glycol monoalkyl ether, 8-50 are preferable and 10-30 are more preferable. The number of carbon atoms in the alkyl group of the polyethylene glycol monoalkyl ether is preferably 1-20, and more preferably 1-12.

  These monomers may be used alone to form a polymer, or two or more may be used in combination to form a polymer. The purpose of the polymer (Tg adjustment, solubility improvement, It can be appropriately selected depending on the dispersion stability and the like.

<< Conventional Polymer >>
In the present invention, a conventionally known polymer (resin) can be used as the resin. Preferred polymers include a polymer containing an acetal group as a main functional group, a polymer containing a carbonate group, and a hydroxyl group. And a polymer having an ester group, and particularly a polymer containing an acetal group, particularly polyvinyl butyral.

  The above polymer may have a substituent, and the substituent may have a linear, branched, or cyclic structure. Various polymers having the above functional groups are commercially available, but can also be synthesized by a conventional method. These copolymers can also be obtained, for example, by introducing an epoxy group into one polymer molecule and later performing polycondensation with another polymer or graft polymerization using light or radiation.

  A polymer obtained by radical polymerization of a vinyl monomer having a polymerizable ethylenically unsaturated double bond is also preferably used. Polymers obtained by radical polymerization such as ethylene, propylene, butadiene, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, (meth) acrylic acid esters, acrylic acid, methacrylic acid, acrylamides, such as styrene / ethyl acrylate, Alternatively, a copolymer polymer such as butyl acrylate, a copolymer polymer such as styrene / ethyl hexyl methacrylate, and a copolymer polymer such as styrene / ethyl hexyl methacrylate / hydroxyethyl acrylate are exemplified.

  In the preparation of the core-shell type colored fine particles according to the present invention, a particularly preferred polymer is a polymer containing an acetal group (polyvinyl acetal). Among them, in particular, polyvinyl butyral has a solubility and affinity for a dye such as a dye. It is preferable in terms of interaction, and one of a plurality of resins used for forming the core is preferably polyvinyl butyral. In addition, one or more of the above polymers are different from polyvinyl butyral. It is preferable to mix and use as a resin component. Moreover, even if it is the same kind of polyvinyl butyral resin, you may combine the thing from which an average degree of polymerization differs, a thing from which molecular weight distribution differs, etc.

(Molecular weight of resin)
These resins (polymers) used in the present invention have a number average molecular weight of 500 to 100,000, particularly 1,000 to 30,000. It is preferable from the point of formability.

(Glass transition point of resin (Tg))
As the glass transition point (Tg) of the resin, various types can be used. Among the polymers to be used, it is preferable to use at least one polymer having a Tg of 10 ° C. or more.

<< Lipophilic solvent >>
The organic solvent (lipophilic solvent) used for the preparation of the fine particle dispersion according to the present invention will be described.

  In the present invention, “lipophilic” refers to a solvent having the above-mentioned LogP value of 0 or more.

  Specific examples of lipophilic solvents (also referred to as hydrophobic solvents) used in the present invention include alcohols (eg, pentanol, heptanol, octanol, phenylethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, anil alcohol). , Cetyl alcohol, oleyl alcohol, octadecyl alcohol, etc.), esters (ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, propylene glycol diacetate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, benzyl acetate , Phenylethyl acetate, phenoxyethyl acetate, ethyl phenylacetate, benzyl propionate, ethyl benzoate, butyl benzoate, butyric laurate , Isopropyl myristate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, diethyl phthalate, dibutyl phthalate, diundecyl phthalate, diethyl malonate, dipropyl malonate Diethyl diethyl malonate, diethyl succinate, dibutyl succinate, diethyl glutarate, diethyl adipate, dipropyl adipate, dibutyl adipate, di (2-methoxyethyl) adipate, diethyl sebacate, diethyl maleate, maleic acid Dibutyl, dioctyl maleate, diethyl fumarate, dioctyl fumarate, cinnamic acid-3-hexenyl, tributyl citrate, etc.), ethers (eg, butyl phenyl ether, benzyl ethyl ether, hexyl ether) Etc.), ketones (eg benzyl methyl ketone, benzyl acetone, diacetone alcohol, cyclohexanone etc.), hydrocarbons (eg petroleum ether, petroleum benzyl, tetralin, decalin, tertiary amylbenzene, dimethylnaphthalene etc.), Amides (for example, N, N-diethyldodecanamide, N, N-dibutyldodecanamide, etc.) can be mentioned.

  In the present invention, when a high-boiling organic solvent having a boiling point of 150 ° C. or higher is contained, it is one of preferred embodiments in terms of color tone or dispersion stability. The high-boiling organic solvent is preferably 1 to 1000% by mass, more preferably 10 to 400% by mass, based on the oil-soluble dye. A high boiling point organic solvent may be used individually by 1 type, and may use 2 or more types together. The boiling point of the high-boiling organic solvent needs to be 150 ° C. or higher, and is preferably 170 ° C. or higher. The dielectric constant of the high-boiling organic solvent needs to be 3 to 12, and preferably 4 to 10. Here, the dielectric constant represents the relative dielectric constant with respect to the vacuum at 25 ° C.

  The high-boiling organic solvent can also be used in the above-described pigment dispersion in which an oil-soluble pigment is dispersed in an aqueous medium. That is, the dye dispersion may have a form in which the oil-soluble dye dissolved in a high boiling point organic solvent is dispersed in an aqueous medium.

  The high boiling point organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include compounds described in U.S. Pat. No. 2,322,027, including phosphate esters, High-boiling organic solvents such as fatty acid esters, phthalic acid esters, benzoic acid esters, phenols and amides are preferred.

  By using the high-boiling organic solvent, the solubility of the dye in the polymer is improved, the color tone becomes better, and the effect of improving the dispersion stability is also obtained.

  These high boiling point organic solvents may be used alone or in combination of two or more. For example, combined use of tricresyl phosphate and dibutyl phthalate, trioctyl phosphate and di (2-ethylhexyl). ) Combined use with sebacate, combined use of dibutyl phthalate and poly (Nt-butylacrylamide).

  In the present invention, a low-boiling organic solvent (an organic solvent having a boiling point of 150 ° C. or lower (usually about 30 ° C. or higher) at normal pressure) can be used in combination with the high-boiling organic solvent. The above lipophilic solvent (high boiling organic solvent, low boiling organic solvent) can be used by dissolving the compound represented by the general formula [1] as it is, and a resinous dispersant or binder can be used. It can also be used in combination by dispersing or dissolving.

  For the specific method for preparing the oil-based solvent used in such an ink jet recording liquid, the methods described in JP-A-3-231975 and JP-A-5-508883 can be referred to.

(Solid solvent (also called phase change solvent))
The solid (phase change) solvent used in the present invention is a phase change solvent which is a solid at room temperature as a solvent and is in a molten liquid state when the inkjet recording liquid is heated and jetted.

  Such phase change solvents include natural waxes (eg, beeswax, carnauba wax, rice wax, wood wax, jojoba oil, whale wax, candelilla wax, lanolin, montan wax, ozokerite, ceresin, paraffin wax, microwax. Crystallin wax, petrolactam, etc.), polyethylene wax derivatives, chlorinated hydrocarbons, organic acids (eg palmitic acid, stearic acid, behenic acid, tiglic acid, 2-acetonaphthone behenic acid, 12-hydroxystearic acid, dihydroxystearic acid) Acid), organic acid esters (for example, esters of the above-mentioned organic acids with alcohols such as glycerin, diethylene glycol, and ethylene glycol), alcohols (for example, dodecanol, tetradecanol, hexadecanol, eicosano) , Docosanol, tetracosanol, hexacosanol, octacosanol, dodecenol, myricyl alcohol, tetrasenol, hexadecenol, eicosenol, docosenol, pinene glycol, hinokiol, butynediol, nonanediol, isophthalyl alcohol, mesythelin, teleaphthalyl alcohol , Hexanediol, decanediol, dodecanediol, tetradecandiol, hexadecanediol, docosandiol, tetracosanediol, tvneol, phenylglycerin, eicosanediol, octanediol, phenylpropylene glycol, bisphenol A, paraalphacumylphenol Etc.), ketones (eg benzoylacetone, diacetobenzene, benzophenone, tricho Non, heptacosanone, heptatriacontanone, hentriacontanone, heptatriacontanone, stearone, laurone, dianisole, etc.), amides (eg oleic acid amide, lauric acid amide, stearic acid amide, ricinoleic acid amide, palmitic acid amide) , Tetrahydrofuranic acid amide, erucic acid amide, myristic acid amide, 12-hydroxystearic acid amide, N-stearyl erucic acid amide, N-oleyl stearic acid amide, N, N'-ethylenebislauric acid amide, N, N'- Ethylene bis stearic acid amide, N, N'-ethylene bis oleic acid amide, N, N'-methylene bis stearic acid amide, N, N'-ethylene bis behenic acid amide, N, N'-xylylene bis stearic acid amide , N, N'-Buchi Lenbis stearic acid amide, N, N′-dioleyl adipic acid amide, N, N′-distearyl adipic acid amide, N, N′-dioleyl sebacic acid amide, N, N′-cysteallyl sebacic acid amide, Like N, N'-distearyl terephthalamide, N, N'-distearylisophthalamide, phenacetin, toluamide, acetamide, oleic acid dimer / ethylenediamine / stearic acid (1: 2: 2 molar ratio) A reaction product of dimer acid, diamine and fatty acid such as tetraamide), sulfonamide (eg, paratoluenesulfonamide, ethylbenzenesulfonamide, butylbenzenesulfonamide, etc.), silicones (eg, silicone SH6018 (Toray Silicone), Silicone KR215, 216, 220 (Shin-Etsu Corn), etc.), coumarones (for example, Escron G-90 (Nippon Chemical Co., Ltd.)), cholesterol fatty acid esters (for example, stearic acid cholesterol, palmitic acid cholesterol, myristic acid cholesterol, behenic acid cholesterol, lauric acid cholesterol, melisin) Acid cholesterol, etc.), saccharide fatty acid esters (sucrose stearate, sucrose palmitate, saccharose behenate, saccharose laurate, saccharose melicate, lactose stearate, lactose palmitate, lactose myristate, lactose behenate, lactose laurate, melicine Acid lactose, etc.).

  The phase change temperature in the solid-liquid phase change of the solid (phase change) solvent is preferably 60 to 200 ° C, and more preferably 80 to 150 ° C.

  The solid (phase change) solvent as described above can be used by dissolving the dye of the present invention as it is in a heated molten solvent, and can also be dispersed or dissolved in combination with a resinous dispersant or binder. It can also be used.

  For a specific method for preparing such a phase change solvent, methods described in JP-A Nos. 5-186723 and 7-70490 can be referred to.

The ink jet recording liquid of the present invention using the water-based, oil-based, solid (phase change) solvent as described above and dissolving the dye of the present invention preferably has a viscosity at the time of flight of 40 × 10 ⁻³ Pa · s or less. 30 × 10 ⁻³ Pa · s or less is more preferable.

The ink jet recording liquid of the present invention is preferably ^{20 × 10 -5 N / cm~100 ×} 10 -5 N / cm surface tension at the time of ^{flight, 30 × 10 -5 N / cm~80} × 10 - More preferably, it is ⁵ N / cm.

  The resin-type dispersant used in the present invention is preferably a polymer compound having a molecular weight of 1,000 to 1,000,000. When these are used, 0.1 to 50% by mass in the ink jet recording liquid is used. It is preferable to contain.

  The inkjet recording liquid of the present invention includes a viscosity modifier, a surface tension adjuster, a ratio according to the purpose of improving ejection stability, compatibility with print heads and ink cartridges, storage stability, image storage stability, and other various performances. Resistance adjusting agents, film forming agents, dispersants, surfactants, ultraviolet absorbers, antioxidants, fading inhibitors, antifungal agents, rust inhibitors, and the like can also be added.

(Inkjet recording method)
The ink jet recording method used in the present invention will be described.

  The ink jet recording liquid of the present invention is not particularly limited with respect to the recording method used, but can be preferably used as an ink jet recording liquid for an on-demand ink jet printer. As an on-demand type, an electro-mechanical conversion type (for example, a single cavity type, a double cavity type, a bender type, a piston type, a shear mode type, a shared wall type, etc.), an electro-thermal conversion type (for example, a thermal type) Specific examples include an ink jet type, a bubble jet (R) type, an electrostatic attraction method (for example, an electric field control type, a slit jet type, etc.), and a discharge method (for example, a spark jet type). .

(Thermal transfer recording material)
Next, the thermal transfer recording material of the present invention will be described. The thermal transfer recording material of the present invention is characterized by using the compound represented by the general formula [1]. When the compound (or dye) of the present invention is used in a thermal transfer recording material, it is preferably contained in a thermal transfer dye donating material. The thermal transfer dye donating material can be used in the form of a sheet, continuous roll or ribbon. The thermal transfer dye-donating material has a support and a dye-donating layer.

  In the thermal transfer dye-providing material, each dye is usually placed on a support so as to form an independent area. For example, each dye region is arranged on a single support in a surface sequential manner or a line sequential manner. It is also possible to prepare a thermal transfer dye donating material in which each dye is provided on a separate support, and sequentially transfer the dye to one thermal transfer image receiving material.

The dye of the present invention is preferably dissolved or dispersed in a suitable solvent together with the binder resin and coated on the support, or printed on the support by a printing method such as a gravure method. The thickness of the dye-donating layer containing the dye is usually preferably set in the range of about 0.2 to 5 μm, particularly preferably in the range of 0.4 to 2 μm in terms of dry film thickness. The coating amount of the thermal transfer dye of the present invention is preferably ^{0.03~1g / m 2, 0.1~0.6g / m} 2 is more preferable.

  As the binder resin, any binder resin that is conventionally known for such purposes can be used, and one that has high heat resistance and that does not hinder migration of the dye when heated is selected. The For example, polyamide resins, polyester resins, epoxy resins, polyurethane resins, polyacryl resins (for example, polymethyl methacrylate, polyacrylamide, polystyrene-2-acrylonitrile), vinyl resins such as polyvinyl pyrrolidone, poly Vinyl chloride resin (for example, vinyl chloride-vinyl acetate copolymer), polycarbonate resin, polystyrene, polyphenylene oxide, cellulose resin (for example, methyl cellulose, ethyl cellulose, carboxymethyl cellulose, cellulose acetate hydrogen phthalate, cellulose acetate, cellulose acetate pro Pionate, cellulose acetate butyrate, cellulose triacetate), polyvinyl alcohol resin (for example, polyvinyl alcohol, polyester Vinyl acetal, partially saponified polyvinyl alcohol such as polyvinyl butyral), petroleum resins, rosin derivatives, coumarone - indene resins, terpene resins, polyolefin resins (e.g., polyethylene, polypropylene) and the like.

  The binder resin in the present invention is preferably used, for example, at a ratio of about 20 to 600 parts by mass per 100 parts by mass of the dye. As the ink solvent used for dissolving or dispersing the coloring matter and the binder resin in the present invention, any conventionally known ink solvent can be used.

  Any conventionally known support can be used as the support for the thermal transfer dye donating material. For example, polyethylene terephthalate; polyamide; polycarbonate; glassine paper; condenser paper; cellulose ester; fluorine polymer; polyether; polyacetal; The thickness of the support for the thermal transfer dye donating material is generally 2 to 30 μm.

  The support may be provided with an undercoat layer as necessary. Further, a dye diffusion preventing layer made of a hydrophilic polymer may be provided between the support and the dye donating layer. This further improves the transfer density. As the hydrophilic polymer, the aforementioned water-soluble polymer can be used. A slipping layer may be provided to prevent the thermal head from sticking to the dye-donating material. The slipping layer is composed of a lubricating material containing a polymer binder or a non-containing lubricating material such as a surfactant, a solid or liquid lubricant, or a mixture thereof.

  The thermal transfer dye-providing material is preferably subjected to a sticking-preventing treatment on the side of the support on which the dye-donating layer is not provided, in order to prevent sticking due to the heat of the thermal head when printing from the back side and to improve sliding. . For example, (1) a reaction product of polyvinyl butyral resin and isocyanate, (2) an alkali metal salt or alkaline earth metal salt of a phosphate ester, and (3) a heat-resistant slip layer mainly composed of a filler is provided. Good.

  The polyvinyl butyral resin has a molecular weight of about 60 to 200,000, a glass transition point of 80 to 110 ° C., and a mass% of vinyl butyral portion of 15 to 40% from the viewpoint of many reaction sites with isocyanate. Things are good. As the alkali metal salt or alkaline earth metal salt of the phosphoric acid ester, Gafac RD720 manufactured by Toho Chemical Co., Ltd. is used, and it is used in an amount of 1 to 50% by mass, preferably about 10 to 40% by mass with respect to the polyvinyl butyral resin. Good. The heat resistant slip layer preferably has heat resistance in the lower layer, and a combination of a synthetic resin that can be cured by heating and a curing agent thereof, such as polyvinyl butyral and polyvalent isocyanate, acrylic polyol and polyvalent isocyanate, cellulose acetate and titanium chelate. A combination of an agent or a polyester and an organic titanium compound may be provided by coating.

  The thermal transfer dye donating material may be provided with a hydrophilic dye barrier layer in order to prevent the dye from diffusing toward the support. The hydrophilic dye barrier layer preferably contains a hydrophilic substance useful for the intended purpose. Generally, gelatin, poly (acrylamide), poly (isopropylacrylamide), butyl methacrylate graft gelatin, ethyl methacrylate graft gelatin, cellulose monoacetate, methylcellulose, poly (vinyl alcohol), poly (ethyleneimine), poly (acrylic acid) ), Using a mixture of poly (vinyl alcohol) and poly (vinyl acetate), a mixture of poly (vinyl alcohol) and poly (acrylic acid), or a mixture of cellulose monoacetate and poly (acrylic acid) Results are obtained. Particularly preferred are poly (acrylic acid), cellulose monoacetate or poly (vinyl alcohol).

The thermal transfer dye donating material may be provided with an undercoat layer. In the present invention, any undercoat layer may be used as long as it has a desired action. Preferred examples include (acrylonitrile-vinylidene chloride-acrylic acid) copolymer (mass ratio 14: 80: 6), (butyl acrylate). -Methacrylic acid-2-aminoethyl-methacrylic acid-2-hydroxyethyl) copolymer (mass ratio 30:20:50), linear / saturated polyester such as Bostic 7650 (Mhart, Bostic Chemical Group) Or a chlorinated high density poly (ethylene-trichloroethylene) resin is mentioned. Although there is no special restriction | limiting in the application quantity of the said undercoat, Usually, it uses in the quantity of 0.1-2.0 g / m < ² >.

  In the present invention, the thermal transfer dye-donating material is superposed on the thermal transfer image-receiving material, and thermal energy corresponding to the image information is applied from either side, preferably from the back side of the thermal transfer dye-donating material, by a heating means such as a thermal head. By applying, the dye of the dye-donating layer can be transferred to the thermal transfer image-receiving material according to the magnitude of the heating energy, and a color image with excellent sharpness and resolution gradation can be obtained. In addition, the anti-fading agent can be transferred in the same manner.

  The heating means is not limited to a thermal head, and known devices such as a laser beam (for example, a semiconductor laser) infrared flash and a thermal pen can be used. In a system using a laser, the thermal transfer dye donating material preferably contains an absorptive material that strongly absorbs a laser beam. Examples of the absorbent material include U.S. Pat. Nos. 4,973,572, 4,948,777, 4,948,778, 4,948,776, 4,942,141, Preferred examples include carbon blacks and infrared absorbing cyanine dyes described in each specification of 4,952,552, 5,036,040, 4,912,083, 6,197,474, and the like. It is done.

  When the thermal transfer dye-donating material is irradiated with a laser beam, the absorbing material converts light energy into heat energy and immediately transfers the heat to a nearby dye, thereby transferring the heat to the image receiving material. Heated to transition temperature. The absorbent material is preferably present in a layered state and / or mixed with the dye below the dye. The laser beam is modulated with an electrical signal representing the shape and color of the original image, and only the areas of the dye that need to be present on the thermal transfer dye-donor material to reconstruct the original color of the object are heated and heat transferred. . A more detailed description of this process is given in GB 2,083,726A. In British Patent 2,083,726A, the absorbing material disclosed for the laser system is carbon. In the present invention, the thermal transfer dye-donating material is combined with the thermal transfer image receiving material to produce images using various thermal printing printers, facsimiles, magnetic recording methods, optical recording methods, image printing, televisions, CRTs, etc. It can be used to make prints from the screen. For details of the thermal transfer recording method, reference can be made to JP-A-60-34895.

  In a preferred embodiment of the present invention, the thermal transfer dye-donating material comprises a polyethylene terephthalate support coated with the thermal transfer dye of the present invention, and a transfer image is formed by carrying out the above-described steps. Thermal transfer of the dye from the thermal transfer dye-donating material to the receiver material can be accomplished by ion gas lasers such as argon and krypton, metal vapor lasers such as copper, gold and cadmium, solid state lasers such as ruby and YAG, or 750-870 nm. Several types of lasers such as semiconductor lasers such as gallium arsenide that emit in the infrared region can be used. In practice, however, semiconductor lasers are advantageous in terms of small size, low cost, stability, reliability, durability, and ease of modulation.

  The thermal transfer image-receiving material used in combination with the thermal transfer dye-donating material is provided with an image-receiving layer for receiving a dye transferred from the thermal transfer dye-donating material on a support. The image receiving layer accepts a heat transferable dye transferred from a thermal transfer dye donating material during printing, and a substance capable of receiving a heat transferable dye having a function of dyeing the heat transferable dye. Or a film having a thickness of about 0.5 to 50 μm which is contained together with other binder substances. The following resin is mentioned as a polymer which is a typical example of the substance which can receive the said heat transferable pigment | dye.

  (I) As those having an ester bond, dicarboxylic acid components such as terephthalic acid, isophthalic acid, and succinic acid (these dicarboxylic acid components may be substituted with sulfo groups, carboxyl groups, etc.) and ethylene glycol, Polyester resin obtained by condensation of propylene glycol, neopentyl glycol, bisphenol A, etc .: polyacrylic ester resin such as polymethyl methacrylate, polybutyl methacrylate, polymethyl acrylate, polybutyl acrylate, or polymethacrylic ester resin: polycarbonate resin: Examples thereof include polyvinyl acetate resin: styrene acrylate resin: vinyl toluene acrylate resin. Specific examples include those described in JP-A Nos. 59-101395, 63-7971, 63-7972, 63-7773, and 60-294862. Commercially available products may include Byron 290, Byron 200, Byron 280, Byron 300, Byron 103, Byron GK-140, Byron GK-130, Kao ATR-2009 and ATR-2010 manufactured by Toyobo.

  (B) Examples of those having a urethane bond include polyurethane resins.

  (C) Examples of those having an amide bond include polyamide resins.

  (D) Examples of those having a urea bond include urea resins.

  (E) Examples of those having a sulfone bond include polysulfone resins.

  (F) Others having a highly polar bond include polycaprolactone resin, styrene-maleic anhydride resin, polyacrylonitrile resin, and the like.

In addition to the synthetic resin, a mixture or copolymer thereof can also be used. Further, basic compounds and / or mordants described in JP-A-1-188391 and 3-83855 can also be used. (Hereinafter, the basic compound and the mordant will be referred to as a dye fixing agent.)
As the dye fixing agent, a compound having a primary to tertiary amino group (more preferably a compound having a tertiary amino group), a compound having a nitrogen-containing heterocyclic group, and a compound having a quaternary cationic group are preferable. . Among these, a polymer dye fixing agent is particularly preferable.

  The other polymer component is preferably a vinyl compound, and more specifically, methacrylic acid esters, acrylic acid esters, styrenes, heterocyclic vinyls and the like. These other monomers are used in a range not exceeding 90 mol% in the total polymer component of the polymer dye fixing agent.

  Specific examples of the polymer dye fixing agent used in the present invention are listed below, but are not limited thereto.

  Specific examples of homopolymers and copolymers containing vinyl monomer units having a tertiary imidazole group include the specifications of US Pat. Nos. 4,282,305, 4,115,124, and 3,148,061. And dye fixing agents described in JP-A-60-118834, JP-A-60-122941, JP-A-62-244043, and JP-A-62-244036. Preferable specific examples of homopolymers and copolymers containing vinyl monomer units having a quaternary imidazolium salt include British Patent Nos. 2,056,101, 2,093,041, 1,594,961, US Patents 4,124,386, 4,115,124, 4,273,853, 4,450,224, JP-A-48-28325, etc. Dye fixing agents. Other preferred specific examples of homopolymers and copolymers containing vinyl monomer units having a quaternary ammonium salt include those described in U.S. Pat. Nos. 3,709,690, 3,898,088, and 3,958,995. Examples thereof include dye fixing agents described in JP-A-60-57836, JP-A-60-60643, JP-A-60-122940, JP-A-60-122942, and JP-A-60-235134. .

The molecular weight of the polymer dye fixing agent in the present invention is preferably 1 × 10 ³ to 1 × 10 ⁶ , particularly preferably 1 × 10 ⁴ to 2 × 10 ⁵ . The polymer dye fixing agent may form a receiving layer alone. Moreover, it can also be used by mixing with the synthetic resin described below. The coating amount of the polymeric dye fixing agent is preferably 0.2 to 30 g / m ^2, more preferably 0.5 to 15 g / m ^2. 0-120 degreeC is preferable and, as for Tg of the said polymer dye fixing agent, 30-70 degreeC is more preferable. The polymer dye fixing agent is preferably a polymer having a tertiary amino group, and more preferably a polymer having a tertiary amino group as a pendant.

  The polymer dye fixing agent is preferably easily soluble in an organic solvent that does not substantially contain water. Examples of the organic solvent include toluene, xylene, methylene chloride, chloroform dichloroethane, hexane, pentane, acetone, cyclohexane, methyl ethyl ketone, ethyl acetate, butyl acetate, dimethylacetamide, dimethylformamide, methanol, ethanol, isopropanol, acetonitrile, propionitrile, Examples include terahydrofuran and diethyl ether.

  The most preferable polymer dye fixing agent is a derivative of polyvinyl alcohol having a tertiary amino group as a pendant. In addition, the mixing ratio when used in combination with a synthetic resin can be easily determined by those skilled in the art according to the type and composition of the polymer dye fixing agent and the applied image forming process. The synthetic resin ratio is preferably 10/90 to 100/0. The synthetic resin is not particularly limited as long as it accepts a dye transferred from the transfer sheet, and specifically, the above-described synthetic resins (A) to (F) are used.

  In the thermal transfer image-receiving material, particularly in the image-receiving layer, a high-boiling organic solvent or a thermal solvent can be contained as a substance capable of receiving a heat-transferable dye or as a dye diffusing agent. Specific examples of the high boiling point organic solvent and the thermal solvent include JP-A Nos. 62-174754, 62-245253, 61-209444, 61-200538, 62-8145, and 62. And the compounds described in JP-A Nos. 9348, 62-30247, and 62-136646.

  The image-receiving layer of the thermal transfer image-receiving material in the present invention may be configured to carry a substance capable of receiving a heat-transferable dye dispersed in a water-soluble binder. As the water-soluble binder used in this case, various known water-soluble polymers can be used, and a water-soluble polymer having a group capable of undergoing a crosslinking reaction with a hardener is preferable. The image receiving layer may be composed of two or more layers. When it is composed of two or more layers, a synthetic resin having a low glass transition point is used for the layer closer to the support, or the dyeing property to the dye is enhanced by using a high boiling point organic solvent or a thermal solvent. In the outermost layer, use a synthetic resin with a higher glass transition point, minimize the use of high boiling point organic solvents and thermal solvents, or avoid stickiness on the surface, adhesion with other substances, It is desirable to prevent the failure such as retransfer to another substance after transfer and blocking with a thermal transfer dye donating material. The total thickness of the image receiving layer is preferably in the range of 0.5 to 50 μm, particularly preferably in the range of 3 to 30 μm. In the case of a two-layer structure, the outermost layer is preferably in the range of 0.1 to 2 μm, and particularly preferably in the range of 0.2 to 1 μm.

  The thermal transfer image receiving material in the present invention may have an intermediate layer between the support and the image receiving layer. The intermediate layer is either a cushion layer, a porous layer, a dye diffusion preventing layer, or a layer having two or more of these functions, depending on the material constituting the material. In some cases, the intermediate layer also serves as an adhesive. The dye diffusion preventing layer serves to prevent the heat transferable dye from diffusing to the support. The binder constituting the diffusion preventing layer may be water-soluble or organic solvent-soluble, but a water-soluble binder is preferable. As a specific example thereof, the water-soluble binder mentioned as the binder for the image receiving layer, particularly gelatin is preferable. The porous layer is a layer that prevents heat applied at the time of thermal transfer from diffusing from the image receiving layer to the support and plays a role of effectively using the applied heat.

  In the present invention, the image receiving layer, cushion layer, porous layer, diffusion preventing layer, adhesive layer, etc. constituting the thermal transfer image receiving material are silica, clay, talc, diatomaceous earth, calcium carbonate, calcium sulfate, barium sulfate, aluminum silicate. Further, fine powders such as synthetic zeolite, zinc oxide, lithobon, titanium oxide, and alumina may be contained.

  The support used for the thermal transfer image-receiving material in the present invention can withstand the transfer temperature and satisfy the requirements in terms of smoothness, whiteness, slipperiness, friction, antistatic properties, dents after transfer, and the like. Anything can be used. For example, synthetic paper (synthetic paper such as polyolefin and polystyrene), fine paper, art paper, coated paper, cast coated paper, wallpaper, backing paper, synthetic resin or emulsion impregnated paper, synthetic rubber latex impregnated paper, synthetic resin Paper support such as paper, paperboard, cellulose fiber paper, polyolefin coated paper (especially paper coated on both sides with polyethylene), various plastic films or sheets such as polyolefin, polyvinyl chloride, polyethylene terephthalate, polystyrene, methacrylate, polycarbonate And a film or sheet treated to give white plasticity to this plastic. Moreover, the laminated body by said arbitrary combinations can also be used.

  A fluorescent whitening agent may be used for the thermal transfer image receiving material. As an example, K.K. Examples thereof include compounds described in “The Chemistry of Synthetic Dies” edited by Vevkataramaman, Vol. 5, Chapter 8, Japanese Patent Application Laid-Open No. 61-143752. More specifically, stilbene compounds, coumarin compounds, biphenyl compounds, benzoxazolyl compounds, naphthalimide compounds, pyrazoline compounds, carbostyryl compounds, 2,5-dibenzoxazole thiophene compounds, and the like. Can be mentioned. The fluorescent brightening agent can be used in combination with an anti-fading agent.

  In the present invention, in order to improve the releasability between the thermal transfer dye-donating material and the thermal transfer image-receiving material, in the layer constituting the dye-donating material and / or the image-receiving material, particularly the outermost layer corresponding to the surface where both materials are in contact with each other. It is preferable to contain a release agent.

  Examples of the release agent include solid or waxy substances such as polyethylene wax, amide wax, and Teflon (R) powder: surfactants such as fluorine-based and phosphoric ester-based: paraffin-based, silicone-based, and fluorine-based oils Any conventionally known release agent can be used, and silicone oil is particularly preferable. As the silicone oil, modified silicone oils such as carboxy-modified, amino-modified, and epoxy-modified can be used in addition to the unmodified one. Examples thereof include various modified silicone oils described on pages 6 to 18B of “Modified Silicone Oil” technical data issued by Shin-Etsu Silicone Co., Ltd. When used in an organic solvent-based binder, an amino-modified silicone oil having a group capable of reacting with the crosslinking agent of the binder (for example, a group capable of reacting with isocyanate) is also emulsified and dispersed in a water-soluble binder. In this case, carboxy-modified silicone oil (for example, trade name X-22-3710 manufactured by Shin-Etsu Silicone Co., Ltd.) is effective.

  The layer constituting the thermal transfer dye donating material and the thermal transfer image receiving material used in the present invention may be cured with a hardener. In the case of curing an organic solvent-based polymer, hardeners described in JP-A-61-199997 and JP-A-58-215398 can be used. For polyester resins, it is particularly preferable to use an isocyanate-based hardener. The curing of the water-soluble polymer is described in US Pat. No. 4,678,739, column 41, JP-A Nos. 59-116655, 62-245261, 61-18942, and the like. Hardeners are suitable for use. More specifically, aldehyde hardeners (formaldehyde, etc.), aziridine hardeners, epoxy hardeners, vinyl sulfone hardeners (N, N'-ethylene-bis (vinylsulfonylacetamide) Ethane), N-methylol hardeners (dimethylolurea, etc.), or polymer hardeners (compounds described in JP-A-62-234157).

  An anti-fading agent may be used for the thermal transfer dye donating material and the thermal transfer image receiving material. As the anti-fading agent, the aforementioned compounds can be used.

  In the constituent layers of the thermal transfer dye donating material and the thermal transfer image receiving material, various surfactants can be used for the purpose of coating aid, peelability improvement, smoothness improvement, antistatic and development promotion. For example, saponins (steroidal), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol alkyl ethers, polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkyl amines or amides, Polyethylene oxide adducts of silicone), glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc .: alkylcarboxylic acids Salt, alkyl sulfonate, alkyl naphthalene sulfonate, alkyl sulfate, alkyl phosphate N-acyl-N-alkyl taurines, sulfosuccinic acid esters, sulfoalkyl polyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphoric acid esters, carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate esters Anionic surfactants containing acidic groups such as amino acids: double-sided surfactants such as amino acids, aminoalkylsulfonic acids, aminoalkylsulfuric acid or phosphate esters, alkylbetaines, amine oxides: alkylamine salts, aliphatic or Cationic surfactants such as aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as biridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used. Specific examples of these are described in JP-A Nos. 62-173463 and 62-183457.

  When dispersing substances that can accept heat transfer dyes, mold release agents, anti-fading agents, UV absorbers, fluorescent brighteners, and other hydrophobic compounds in water-soluble binders, It is preferred to use an activator. For this purpose, in addition to the above-mentioned surfactants, surfactants described on pages 37 to 38 of JP-A-59-157636 are particularly preferably used.

  The constituent layers of the thermal transfer dye-donating material and the thermal transfer image-receiving material may contain an organic fluoro compound for the purpose of improving smoothness, preventing static charge and improving peelability. Representative examples of the organic fluoro compound include fluorine-based surfactants described in JP-B-57-9053, columns 8 to 17, JP-A-61-1944, and JP-A-62-135826. Or hydrophobic fluorine compounds, such as oily fluorine-type compounds, such as fluorine oil, or solid fluorine compound resins, such as tetrafluoroethylene resin, are mentioned.

  A matting agent can be used for the thermal transfer dye donating material and the thermal transfer image receiving material. As the matting agent, in addition to the compounds described in JP-A-61-88256, page 29, such as silicon dioxide, polyolefin or polymethacrylate, benzoguanamine resin beads, polycarbonate resin beads, AS resin beads, etc. There are compounds described in JP-A-63-274944 and JP-A-63-274952.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these.

Example 1
Synthesis of exemplary compound (20)

  6.7 g of compound (20a) was added to a mixture of 52 ml of acetone and 20 ml of acetic acid, and then a solution containing 4.2 g of concentrated hydrochloric acid and 8.4 g of water was added dropwise over 5 minutes under ice cooling. Further, a solution containing 0.76 g of sodium nitrite and 2.0 g of water was added dropwise at 5 ° C. or less over 15 minutes, and further stirred at 5 ° C. or less for 30 minutes to obtain a diazonium salt. After adding 3.7 g of the compound (20b) to 52 ml of acetone, a solution containing 28.7 g of sodium carbonate and 86 g of water was added and cooled on ice. The diazonium salt prepared above was added over 30 minutes at 5 ° C. or lower while stirring. After stirring at 15 ° C. for 60 minutes, 3.6 g of concentrated hydrochloric acid was added, and the mixture was further stirred at the same temperature for 15 minutes. The precipitated crystals were collected by filtration, washed successively with methanol, water and methanol and then dried. The crude crystals were heated to reflux with methanol to obtain 8.6 g of Exemplified Compound (20). Identification was carried out by MASS and NMR spectra, and it was confirmed to be the exemplified compound (20).

0.2 g of the obtained exemplary compound (20), 2.0 g of tricresyl phosphate, and 0.16 g of sodium dodecylbenzenesulfonate were dissolved in 1.3 g of ethyl acetate. Next, 6.8 g of 15% aqueous solution of lime-processed gelatin and 5.5 g of water were added to 40 ° C. and mixed uniformly, and the mixture was emulsified and dispersed at 40 ° C. and 10000 rpm for 10 minutes using a homogenizer. . In the obtained emulsified dispersion, water was added so that the concentration of the exemplified compound (20) was 0.25 mmol / m ^2, and this was applied onto a photographic paper support using a wire bar. The film formed after application was black.

Example 2
Synthesis of exemplary compound (1)

  After 4.4 g of compound (1a) was added to a mixture of 57 ml of acetone and 20 ml of acetic acid, a solution containing 4.2 g of concentrated hydrochloric acid and 8.4 g of water was added dropwise over 5 minutes under ice cooling. Further, a solution containing 0.76 g of sodium nitrite and 3.0 g of water was added dropwise at 5 ° C. or less over 15 minutes, and further stirred at 5 ° C. or less for 30 minutes to obtain a diazonium salt. After adding 3.7 g of the compound (20b) to 52 ml of acetone, a solution containing 28.7 g of sodium carbonate and 86 g of water was added and cooled on ice. The diazonium salt prepared above was added over 30 minutes at 5 ° C. or lower while stirring. After stirring at 15 ° C. for 60 minutes, 3.6 g of concentrated hydrochloric acid was added, and the mixture was further stirred at the same temperature for 15 minutes. The precipitated crystals were collected by filtration, washed successively with methanol, water and methanol and then dried. The crude crystals were heated to reflux with methanol to obtain 6.5 g of exemplary compound (1). Identification was carried out using MASS and NMR spectra, and it was confirmed to be the exemplified compound (1).

0.2 g of the obtained exemplary compound (1), 2.0 g of tricresyl phosphate, and 0.16 g of sodium dodecylbenzenesulfonate were dissolved in 1.3 g of ethyl acetate. Next, 6.8 g of 15% aqueous solution of lime-processed gelatin and 5.5 g of water were added to 40 ° C. and mixed uniformly, and the mixture was emulsified and dispersed at 40 ° C. and 10000 rpm for 10 minutes using a homogenizer. . In the obtained emulsified dispersion, water was added so that the concentration of the exemplified compound (1) was 0.25 mmol / m ^2, and this was applied onto a photographic paper support using a wire bar. The film formed after application was black.

Example 3
<< Preparation of Inkjet Recording Liquids 1-6: Aqueous Ink >>
The compounds shown in Table 1 were weighed so that the content in the finished ink was 2% by mass, and ethylene glycol 15% by mass, glycerin 15% by mass, Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) 0 3% by mass, adjusted so that the remainder becomes pure water, added with pure water, mixed and dispersed, filtered through a 2 μm membrane filter to remove dust and coarse particles, ink jet recording as shown in Table 1 Liquids 1 to 6 were obtained.

<< Preparation and Evaluation of Image Sample >>
Each ink of the ink jet recording liquids 1 to 6 obtained above is printed on a Konica photo jet paper Photolike QP glossy paper (manufactured by Konica Minolta Photo Imaging Co., Ltd.) using a commercially available Epson ink jet printer (PM-800). The obtained image samples 1 to 6 were evaluated for light resistance of the image, color tone of the image, and ink storage stability as follows.

(Evaluation of light resistance of images)
The obtained sample was irradiated with light with a xenon fade meter for 180 hours, and the light resistance was evaluated by the dye residual ratio of each image. In addition, the dye residual ratio (%) is D0 as the concentration before light irradiation, and D as the concentration after light irradiation.
Light resistance (%) = D / D0 x 100 (%)
Represented by The concentration was measured using a PDA-65 densitometer manufactured by Konica Minolta Photo Imaging Co., Ltd.

(Image tone evaluation)
For each image sample, the average score of the four-point evaluation was calculated by visual evaluation with 10 monitors. If the average score is 2.3 or more, there is no practical problem.

3 points: feels dark black 2 points: feels black 1 point: feels yellowish, reddish, blueish, etc. 0 point: cannot be recognized as black (evaluation of ink storage stability)
After the inkjet recording liquids 1 to 6 were stored in a sealed glass container at 80 ° C. for 1 week, an image was prepared in the same manner as in the preparation of the image sample, and the presence or absence of ejection abnormality during 500 hours of continuous ejection was observed. . The color tone of the image was evaluated based on CIE1976L ^* a ^* b ^* , and the storage stability was evaluated according to the following evaluation criteria.

○: No abnormality in continuous ejection, color change from unstored ink is less than ± 10 for both a ^* and b ^* ×: Color change from unstored ink in which abnormality is observed in continuous ejection is a ^* or b ^In at least one of ^* , 10 or more absolute values are recognized. The obtained results are shown in Table 1.

  From Table 1, it is clear that the image sample of the present invention has better light resistance and color tone of the image than the comparative image sample, and the ink of the present invention also has good ink storage stability.

Example 4
<< Preparation of fine particle dispersion >>
10 g of the compound described in Table 2, 20 g of methyl ethyl ketone, 5 g of glycerin, 6 g of a copolymer (styrene / acrylic acid / 2-hydroxyethyl methacrylate = 80/5/15, neutralized resin) 250 g of zirconia beads having an average particle diameter of 0.5 mm was added to a mixed solution of 40 g of ion-exchanged water, and dispersion was performed for 4 hours using a media disperser (System Zeta; manufactured by Ashizawa Corporation). After the completion of dispersion, zirconia beads were separated by filtration to obtain a dispersion. After 40 ml of water was added to the dispersion for dilution, methyl ethyl ketone was removed by distillation under reduced pressure to obtain a fine particle dispersion.

<< Preparation of inkjet recording liquids 7 to 12: Preparation of water-based ink >>
The fine particle dispersion was weighed so that the content of the compound shown in Table 2 was 3% by mass with respect to the finished amount of the inkjet recording liquid, and 15% by mass of ethylene glycol, 15% by mass of glycerin, and triethylene glycol mono Adjusted so that 3% by weight of butyl ether and 0.3% by weight of Surfynol 465 and the remainder become pure water, mixed and dispersed, and then filtered through a 2 μm membrane filter to remove dust and coarse particles. As shown, inkjet recording liquids 7-12 were obtained.

<< Evaluation of storage stability of ink jet recording liquids 7 to 12: change rate of particle diameter, filterability >>
For the inkjet recording liquids 7 to 12, the average particle diameter change rate when stored at 60 ° C. for 7 days and the filterability of the ink after storage were evaluated as follows.

(Change rate of average particle diameter of ink)
Inkjet recording liquids 7 to 12 were each stored at 60 ° C. for 7 days, and the average (volume average) particle diameter of the ink after storage was determined using a laser particle size analysis system manufactured by Otsuka Electronics, and the storage was similarly determined. In this case, the average particle size change rate with respect to the average particle size of the ink was determined by the following formula, and rank evaluation was performed according to the following criteria.

Average particle diameter change rate (%) = {(average particle diameter of ink after storage−average particle diameter of unstored ink) / (average particle diameter of unstored ink)} × 100
×: 10% or more (practical level)
○: 5% to less than 10% (practical acceptable level)
A: Change rate of particle diameter is less than 5% (Evaluation of ink filterability)
After the inkjet recording liquids 7 to 12 were stored at 60 ° C. for 7 days, 5 ml was collected, filtered through a 0.8 μm cellulose acetate membrane filter, and ranked as follows.

◎: Full amount filtered ○: Half amount or more filtered (practical)
×: Filtering was possible with less than half volume (impossible level)
In the present invention, ◎ and ○ are practical levels.

<Preparation of image sample and evaluation of color tone>
Image samples 7 to 12 were prepared in the same manner as in Example 3 using the inks of the inkjet recording liquids 7 to 12 after storage, and the color tone of the images was evaluated. The results are shown in Table 2.

  From Table 2, it can be seen that the ink of the present invention is superior in the average particle diameter change rate of the ink after storage and the filterability of the ink (that is, the storage stability of the ink) compared to the comparative ink, and Even after storage over time, it can be seen that the image sample produced using the ink of the present invention is excellent in terms of the color tone of the image.

Example 5
<< Preparation of Fine Particle Dispersion >>: Core-shell structured particles 5 g of the compound shown in Table 3 and 5 g of polyvinyl butyral (BL-S manufactured by Sekisui Chemical Co., Ltd., average polymerization degree 350) and 50 g of ethyl acetate are placed in a separable flask. Was replaced with N ₂ gas and stirred to completely dissolve the polyvinyl butyral and the compound.

  After dropping 100 g of an aqueous solution containing 2 g of sodium lauryl sulfate, the mixture was emulsified for 300 seconds using an ultrasonic disperser (UH-150 type, manufactured by SMT Co., Ltd.). Thereafter, ethyl acetate was removed under reduced pressure to obtain a core fine particle dispersion (also referred to as a core fine particle dispersion) in which the compound was impregnated in the polyvinyl butyral.

  0.15 g of potassium persulfate was added to the obtained core fine particle dispersion and dissolved, and after heating to 70 ° C. with a heater, a mixed solution of 2 g of styrene and 1 g of 2-hydroxyethyl methacrylate was added dropwise. Then, the reaction was carried out for 7 hours to form a shell polymer layer on the core fine particles to obtain a core-shell type colored fine particle dispersion.

<< Preparation of Inkjet Recording Liquids 13-18: Aqueous Ink >>
The above-mentioned colored fine particle dispersion in which the pigment content is 2% by mass with respect to the finished amount of the ink is weighed, and 15% by mass of ethylene glycol, 15% by mass of glycerin, 3% by mass of triethylene glycol monobutyl ether, Surfinol 465 is adjusted to 0.3% by mass and the remainder is pure water, and pure water is added and mixed and dispersed. The mixture is further filtered through a 2 μm membrane filter to remove dust and coarse particles, and shown in Table 3. Thus, inkjet recording liquids 13 to 18 were obtained.

<< Evaluation of storage stability of inkjet recording liquids 13 to 18: change rate of particle diameter, filterability >>
The ink jet recording liquids 13 to 18 were evaluated in the same manner as in Example 4 for the average particle size change rate when stored at 60 ° C. for 7 days and the filterability of the ink after storage.

<< Preparation of image sample, color tone, light resistance evaluation >>
Image samples 13 to 18 were prepared in the same manner as in Example 3 using the inks of the inkjet recording liquids 13 to 18 after storage, and the color tone of the image and the light resistance of the image were evaluated. The obtained results are shown in Table 3.

  From Table 3, the ink of the present invention has a low rate of change in the average particle size of the ink after storage compared to the comparative ink, and the filterability of the ink (that is, the storage stability of the ink) is good. In addition, it is apparent that an image sample produced using the ink of the present invention is excellent in both color tone and light resistance.

Example 6
<Production of thermal transfer recording material>
(Preparation of ink)
The following raw materials were mixed to obtain a uniform solution ink containing the coloring matter of the present invention.

8 g of the dye of the present invention (described in Table 4)
Polyvinyl butyral resin (BL-1: Sekisui Chemical Co., Ltd.) 5g
200 ml of methyl ethyl ketone
(Preparation of comparative ink)
The following raw materials were mixed to obtain a uniform solution ink containing a pigment outside the present invention.

Dye (Y-1) 4g
Dye (M-1 or M-2) 3g
Dye (C-1) 3g
Polyvinyl butyral resin (BL-1: supra) 5g
200 ml of methyl ethyl ketone
The above ink was applied and dried on a polyethylene terephthalate (PET) base having a thickness of 4.5 μm using a wire bar so that the coating amount after drying was 0.8 g / m ² , and a thermal transfer layer was formed on the PET film. Thermal transfer recording materials 1 to 6 having the above were prepared. A nitrocellulose layer containing a silicon-modified urethane resin (SP-2105: manufactured by Dainichi Seika) is provided on the back surface of the PET base as a sticking prevention layer.

<Production of image receiving material>
Ester-modified silicon (attachment amount: 0.15 g / m ² ) as an image receiving layer on a support laminated with polyethylene on both sides of paper (including white pigment (TiO ₂ ) and bluing agent on one polyethylene layer) The methyl ethyl ketone solution containing the polyester resin contained was applied and dried so that the amount of the polyester resin applied was 5 g / m ² to obtain an image receiving material.

<Production of transfer image>
When the thermal transfer recording material of the thermal transfer recording materials 1 to 6 and the image receiving layer of the image receiving material were overlapped, and a thermal head was applied from the back side of the thermal transfer recording material, image recording was performed under the following recording conditions. With respect to the recording materials 1 to 4, excellent black images having excellent gradation and substantially less change in color tone at high and low density portions were obtained. The maximum density of each image obtained is shown in Table 4.

<Recording conditions>
Recording density of main scanning and sub scanning: 8 dots / mm
Recording power: 0.6 W / dot Heating time: Stepwise adjustment of heating time between 20 msec and 0.2 msec << Light resistance evaluation >>
The obtained transferred image was irradiated with light using a xenon fade meter, and the light resistance was evaluated based on the dye residual ratio of each image. The results of the dye residual ratio are also shown in Table 4. The dye residual ratio (%) is represented by D / D0 × 100, where D0 is the concentration before light irradiation and D is the concentration after light irradiation.

  As shown in Table 4, since the thermal transfer recording material using the dye of the present invention has excellent dye transferability, the image density obtained is higher than that of the comparative transfer recording material, and light resistance is excellent. It can be seen that there is little change in color tone due to irradiation.

Claims (11)

A compound represented by the following general formula [1].

[Wherein, Ar ₁ represents an aryl group or a heterocyclic group, R ₁ represents a hydrogen atom or a substituent, and R ₂ represents a substituent. However, at least one of R ₁ or R ₂ represents a dye moiety having a chromophore. ] The compound represented by the general formula [1] is represented by the following general formula [2].

[In the formula, Ar ₁ represents an aryl group or a heterocyclic group, X represents an oxygen atom or N—R ₅ , R ₃ , R ₄ , R ₅ represent a substituent, and n represents an integer of 1 to 5] Represent. However, at least one of R ₃ , R ₄ or R ₅ represents a dye moiety having a chromophore, and R ₃ and R ₅ may be bonded to each other to form a heterocyclic ring, and when n is 2 or more , R ₄ may be the same or different. ] At least one chromophore of R ₁ or R ₂ represented by the general formula [1] and at least one chromophore of R ₃ , R ₄ or R ₅ represented by the general formula [2] are: The compound according to claim 1 or 2, which is represented by the general formula [3], [4] or [5].

[Wherein, L ₁ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent, and X ₁ represents a coupler residue. ]

[In the formula, L ₂ represents a simple bond or a divalent linking group, R ₇ represents a substituent, m represents an integer of 0 to 7, Y represents an oxygen atom, ═CR ₈ R ₉ — or = NR ₁₀ -is represented, R ₈ , R ₉ and R ₁₀ represent a hydrogen atom or a substituent, and R ₇ , R ₈ , R ₉ and R ₁₀ may be bonded to each other to form a ring. ]

[In the formula, L ₃ represents a simple bond, an arylene group or a heteroarylene group which may have a substituent, X ₂ represents a coupler residue, Z represents —N═ or —CR ₁₁ ═, R ₁₁ represents a hydrogen atom or a substituent. ] The coloring composition characterized by containing at least 1 sort (s) among the compounds of any one of Claims 1-3. An ink jet recording liquid comprising at least one of the compounds according to claim 1. The ink jet recording liquid according to claim 5, wherein the compound according to claim 1 has a sulfo group or a salt thereof. The ink jet recording liquid according to claim 5, wherein the compound according to any one of claims 1 to 3 is contained as a fine particle dispersion. The ink jet recording liquid according to claim 7, wherein the fine particle dispersion contains an oil-soluble polymer. The inkjet recording liquid according to claim 5, comprising a polyhydric alcohol. 10. An ink jet recording method, wherein recording is performed using the ink jet recording liquid according to any one of claims 5 to 9. A thermal transfer recording material comprising at least one of the compounds according to claim 1.